1% checked with "ispell" sep.2003 /hjaaj 2% File: Sirius.tex 3 4\def\mxfelt{20 } % max number of finite fields 5 6 7\chapter{\label{chap:sirius-inpref}Molecular wave functions, {\sir}} 8 9\section{\label{sec:sirius-ref-notes} General notes for the {\sir} input reference 10manual} 11 12{\sir} is the part of the code that computes the wave function/density. 13 14The following sections contain a list of all generally relevant keywords to 15{\sir}, only currently inactive keywords and some special debug 16options are omitted. 17 18\begin{enumerate} 19\item {The input for the wave function section must begin with 20 21\begin{inputex} \begin{verbatim} 22**WAVE FUNCTIONS 23\end{verbatim} \end{inputex} 24 with no leading blanks. The preceding lines in the input file may 25 contain arbitrary information. 26} 27 28\item{Input is directed by keywords which internally are stored 29 in upper case, however, in the input file they may be written in upper, lower, or mixed case. 30 Only the first 7 characters including the prompt are significant. 31 The keywords are divided in a number of main input groups. Each main 32 input group is initiated by a {\starkey}. For example 33 34\begin{inputex} \begin{verbatim} 35*ORBITAL INPUT 36\end{verbatim} \end{inputex} 37 marks the beginning of the input group for orbital input. 38} 39 40\item {The keywords belonging to one of the main input groups begin with 41 the prompt {\dotkey}. 42} 43 44\item {Keywords that are necessary to specify are marked by "Required". 45 For other keywords the default values can be used in ordinary runs. 46} 47 48\item {Any keyword line beginning with a \quotekw{!} or 49 \quotekw{\#} will be treated as a 50 comment line. An illegal keyword will cause a dump of all keywords 51 for the current input section. 52} 53 54\item{A dump of keywords can be obtained in any input section by 55specifying the keyword \quotekw{\Key{OPTIONS}}. For example, the input 56 57\begin{inputex} \begin{verbatim} 58**WAVE FUNCTIONS 59.OPTIONS 60**END OF DALTON INPUT 61\end{verbatim} \end{inputex} 62 63 will cause a dump of all keywords in the main input groups in {\sir}, while 64 65\begin{inputex} \begin{verbatim} 66**Wave functions 67*Orbital input 68.options 69**End of Dalton input 70\end{verbatim} \end{inputex} 71 72 will cause a dump of all keywords in the \quotekw{*ORBITAL INPUT} input group 73 in {\sir} (this is also an example of using mixed case for the keywords). 74} 75 76\item{ The {\sir} input is finished with a line beginning with two stars {\starstarkey}, 77 {\it e.g.} 78 79\begin{inputex} \begin{verbatim} 80**END OF DALTON INPUT 81\end{verbatim} \end{inputex} 82 or {\it e.g.} 83 84\begin{inputex} \begin{verbatim} 85**Properties 86\end{verbatim} \end{inputex} 87 88} 89\end{enumerate} 90 91\pagebreak[3] 92\section{\label{sec:ref-newinp} 93 Main input groups in the **WAVE FUNCTIONS input module} 94 95\noindent 96The main input groups (those with the {\starkey} prompt) are listed here and 97the full descriptions are given in the designated sections. 98 99\noindent 100The first input group is always required in order to specify the type of 101calculation, and follows immediately after the \Sec{*WAVE FUNCTIONS} 102keyword. 103 104%Section~\ref{ref-geninp} \Sec{GENERAL INPUT} 105 106\noindent The remaining input groups may be specified in any 107order. In this chapter they are grouped alphabetically, although 108the short presentation below gather them according to purpose. 109 110%\ifsolvent 111The following two input groups are used to modify the 112molecular environment by adding field-dependent 113terms in the Hamiltonian and by invoking 114the self-consistent reaction field model for solvent 115effects, respectively: 116 117Section~\ref{ref-haminp} \Sec{HAMILTONIAN} 118 119Section~\ref{ref-solinp} \Sec{SOLVENT} 120%\else 121%The following input group describes additional field-dependent 122%terms in the Hamiltonian : 123% 124%Section~\ref{ref-haminp} \Sec{HAMILTONIAN} 125%\fi 126 127\noindent 128The next input group specifies the configurations included 129in the MCSCF, MC--srDFT, CI, and CI--srDFT wave functions: 130 131Section~\ref{ref-wavinp} \Sec{CONFIGURATION INPUT} 132 133\noindent 134The two next groups are used to specify initial orbitals and initial 135guess for the CI vector: 136 137Section~\ref{ref-orbinp} \Sec{ORBITAL INPUT} 138 139Section~\ref{ref-civinp} \Sec{CI VECTOR} 140 141\noindent 142The two following input groups control a second-order MCSCF, MC--srDFT, HF, HF-srDFT, or DFT 143optimization: 144 145Section~\ref{ref-optinp} \Sec{OPTIMIZATION} 146 147Section~\ref{ref-stpinp} \Sec{STEP CONTROL} 148 149\noindent 150The next groups have special input only relevant for the 151specified calculation types: 152 153Section~\ref{ref-rhfinp} \Sec{SCF INPUT}, for \Key{HF}, \Key{DFT}, and \Key{HFsrDFT} 154 155Section~\ref{ref-dftinp} \Sec{DFT INPUT}, for \Key{DFT} 156 157Section~\ref{ref-mp2inp} \Sec{MP2 INPUT}, for \Key{MP2} or \Key{MP2SRDFT} 158 159Section~\ref{ref-nevpt2inp} \Sec{NEVPT2 INPUT}, for \Key{NEVPT2} 160 161Section~\ref{ref-cicinp} \Sec{CI INPUT}, for \Key{CI} 162 163Section~\ref{ref-stexinp} \Sec{STEX INPUT}, for \Key{STEX} 164 165\noindent 166The next section is used to select some types of analysis of the final 167HF, HF-srDFT, DFT, MCSCF, MC--srDFT, CI, or CI--srDFT wave function: 168 169Section~\ref{ref-popinp} \Sec{POPULATION ANALYSIS} 170 171\noindent 172The next section is used to change the default integral transformation 173and specify any final integral transformation after convergence (a 174main Dalton module following {\sir} may need a higher transformation level): 175 176Section~\ref{ref-trainp} \Sec{TRANSFORMATION} 177 178\noindent 179The next two input groups control the amount of printed output and 180collect options not fitting in any of the other groups: 181 182Section~\ref{ref-priinp} \Sec{PRINT LEVELS} 183 184Section~\ref{ref-auxinp} \Sec{AUXILIARY INPUT} 185 186\noindent 187Finally we note that there is an input module controlling the 188calculation of coupled cluster wave functions. This is treated in a 189separate chapter: 190 191Chapter~\ref{ch:CC} \Sec{CC INPUT} 192 193\bigskip 194\noindent 195The wave function input is finished when a line is encountered beginning 196with two stars {\starstarkey}, two examples: 197 198\begin{inputex} \begin{verbatim} 199 **END OF DALTON INPUT 200\end{verbatim} \end{inputex} 201and 202 203\begin{inputex} \begin{verbatim} 204 **MOLORB 205 ... formatted molecular orbitals coefficients 206 **END OF DALTON INPUT 207\end{verbatim} \end{inputex} 208 209\noindent 210The \Sec{*MOLORB} keyword or the \Sec{*NATORB} keyword 211must be somewhere on the input file and be 212followed by molecular orbital coefficients if the option for formatted 213input of molecular orbitals has been specified. Apart from this 214requirement, arbitrary information can be written to the following lines 215of the input file. 216 217 218 219\pagebreak[3] 220\subsection{\label{ref-geninp}\Sec{*WAVE FUNCTIONS}} 221 222{\bf Purpose:} 223 224Specification of which wave function calculation is to be performed. 225 226{\bf Primary keywords, {\color{red} listed in the order the corresponding modules 227 will be executed by the program (if the keyword is set)}: } 228 229\begin{description} 230 231\item[{\color{blue}Single configuration models}] Models with a single configuration SCF (HF, DFT, or HFsrDFT) 232 233\begin{description} 234 235\item[\Key{HF}] 236 Restricted closed-shell, one open-shell, or high-spin spin-restricted Hartree--Fock calculation. 237 \index{HF}\index{SCF}\index{Hartree--Fock}\index{open shell!HF}\index{high spin!HF} 238 (Unrestricted HF is not possible in \dalton.) 239 The occupied orbitals, optimization control etc. are specified in the 240 \quotekw{*SCF INPUT} submodule. \\ 241 Note: you can only specify one of the \quotekw{.HF}, \quotekw{.DFT}, and \quotekw{.HFsrDFT} keywords. 242 243\item[\Key{HFsrDFT}] 244 Long-range Hartree-Fock and short-range DFT (HF-srDFT) calculation. \index{HF-srDFT} 245 (Unrestricted HF-srDFT is not possible in \dalton.) 246 The short-range srDFT functional must be defined with the \quotekw{.SRFUN} keyword in this input section. 247 The occupied orbitals, optimization control etc. are specified in the 248 \quotekw{*SCF INPUT} submodule. \\ 249 Default range-separation is the error function with $\mu = 0.4$, our standard value. 250 The value can be canged with the \quotekw{.ERF} keyword. \\ 251 This option is quite similar to long-range corrected Kohn-Sham functionals, the only difference 252 is that long-range correction is also performed on the correlation funtional. 253 HF-srDFT with srPBEGWS may therefore be expected to give results close to LC-PBE. 254 Note: you can only specify one of the \quotekw{.HF}, \quotekw{.DFT}, and \quotekw{.HFsrDFT} keywords. 255 256\item[\Key{DFT}] \ \\ 257 \kw{READ (LUINP,'(A80)') LINE} \\ 258 Restricted closed-shell, one open-shell, or high-spin spin-restricted Kohn-Sham density functional 259 theory\index{DFT}\index{Kohn--Sham}\index{open shell!DFT}\index{high spin!DFT} 260 (Unrestricted Kohn-Sham DFT is not possible in \dalton.) 261 calculation. On the following line you must specify which 262 functional to use. The occupied orbitals, optimization control 263 etc. are specified in the \quotekw{*SCF INPUT} submodule shared with 264 the \quotekw{.HF} option. The DFT specific input options are 265 collected in the \quotekw{*DFT INPUT} input submodule. 266 Note: you can only specify one of the \quotekw{.HF}, \quotekw{.DFT}, and \quotekw{.HFsrDFT} keywords. 267 268\item[\quotekw{.FC MVO} in \quotekw{*SCF INPUT}] 269 Calculation of modified virtual SCF orbitals after SCF convergence based on the 270 potential determined by the keyword (see comments below). 271 The occupied SCF orbitals are not modified. 272 MVOs are typically used for subsequent CI calculation. 273 {\em Note that this keyword is not located in this module but in the 274 \quotekw{*SCF INPUT} submodule. It is mentioned here to make clear 275 at what point this orbital transformation will be performed, if requested.} 276 Option is incompatible with CC, which requires canonical orbitals. 277 278\item[\Key{SRFUN}] \ \\ 279 \kw{READ (LUINP,'(A80)') LINE} \\ 280 Specification of functional used for \quotekw{.HFSRDFT}, \quotekw{.MP2SRDFT}, \quotekw{.CISRDFT}, 281 and \quotekw{.MCSRDFT} calculations. It is \emph{required} for these calculations, there is not default functional. 282 \index{Short-range functionals!.SRFUN} 283 Note that this keyword must not be specified together with the Kohn--Shan DFT keyword \quotekw{.DFT}. 284 285\item[\Key{HFXFAC}] \ \\ 286 \kw{READ (LUINP,'(A80)') LINE} \\ 287 Specification of the full-range Hartree-Fock like exchange for \quotekw{.HFSRDFT} and \quotekw{.MCSRDFT} calculations. 288 289\item[\Key{STEX}] 290 Static exchange calculation based on an SCF wave function.\index{Static exchange} 291 292\end{description} 293 294\item[{\color{blue} Single configuration based correlation models}] Models based on a single configuration (e.g.\ MP2, CC, and CI with orbitals from a single determinant calculation). 295 296\begin{description} 297 298\item[\Key{MP2}] 299 \index{M{\o}ller-Plesset!second-order, MP2}\ 300 M{\o}ller-Plesset second-order perturbation theory calculation, 301 based on canoncial orbitals from an HF calculation calculation. 302 Calculates second-order energy, second-order natural orbitals\index{natural orbitals!MP2}, 303 and first-order wave function for SOPPA. 304 Requires \quotekw{.HF} or previously calculated canonical HF orbitals. 305 306\item[\Key{MP2srDFT}] 307 \index{M{\o}ller-Plesset!MP2--srDFT}\ 308 M{\o}ller-Plesset second-order perturbation theory calculation with short-range srDFT functionals, 309 based on canoncial orbitals from an HFsrDFT calculation. 310 Calculates second-order energy, second-order natural orbitals\index{natural orbitals!MP2--srDFT}, 311 and first-order wave function for SOPPA--srDFT. 312 Requires \quotekw{.HFsrDFT} 313 or previously calculated canonical HF-srDFT orbitals. 314 315\item[\Key{CC}] 316 \index{Coupled Cluster!CC} 317 Coupled cluster calculation. Automatically activates Hartree--Fock (\quotekw{.HF}). 318 After the Hartree--Fock calculation, 319 the \cc\ module is called to do a coupled cluster (response) calculation. 320 M 321 For further input options for the \cc\ module see Section~\ref{sec:ccgeneral}. 322 323\item[\Key{CC ONLY}] Skip the calculation of a Hartree--Fock wave 324 function, and start directly in the coupled cluster part. Convenient 325 for restarts in the coupled cluster module. 326 327\end{description} 328 329\item[{\color{blue} Multi-configuration models}] CI, MCSCF, NEVPT2, GAS-CI; CI--srDFT, MC--srDFT, srNEVPT2. 330 331\begin{description} 332 333\item[\Key{CI}] 334 \index{Configuration Interaction!CI} 335 Configuration interaction calculation. 336 This CI will be based on the molecular orbitals from one of the SCF options, or 337 read in from file (then they can be from MCSCF, MP2, ...). 338 339\item[\Key{CIsrDFT}] 340 \index{CI--srDFT}\index{Configuration Interaction!CI--srDFT} 341 Long range configuration interaction and short-range DFT (CI--srDFT) calculation. 342 The short-range srDFT functional must be defined with the \quotekw{.SRFUN} keyword in this input section. 343 This CI--srDFT will be based on the molecular orbitals from one of the SCF options, or 344 read in from file (then they can be from MCsrDFT, MP2-srDFT, or in fact also from MCSCF, MP2, ...). 345 Note: you can only specify one of the \quotekw{.CI} and \quotekw{.CIsrDFT} keywords. 346 347\item[\Key{MCSCF}] 348 Multiconfiguration self-consistent field (MCSCF) calculation. CASSCF or RASSCF .\index{MCSCF}\\ 349 It is in most cases recommended that you use initial orbitals from MP2 for faster convergence to 350 the desired state (other initial guesses more often end in a local minimum). 351 For open-shell states not well described with MP2 you may consider using the \quotekw{.CINO} option for initial orbitals.\\ 352 Note: you can only specify one of the \quotekw{.MCSCF} and \quotekw{.MCsrDFT} keywords. 353 354\item[\Key{MCsrDFT}] 355 Long-range MCSCF and short-range DFT (MC--srDFT) calculation. CAS-srDFT or RAS-srDFT.\index{MC--srDFT} 356 The short-range srDFT functional must be defined with the \quotekw{.SRFUN} keyword in this input section. 357 Default range-separation is the error function with $\mu = 0.4$, our standard value. 358 The value can be canged with the \quotekw{.ERF} keyword. \\ 359 It is normally recommended that you use initial orbitals from MP2-srDFT for faster convergence to 360 the desired state (other initial guesses more often end in a local minimum). \\ 361 Note: you can only specify one of the \quotekw{.MCSCF} and \quotekw{.MCsrDFT} keywords. 362 363\item[\Key{VIRTRUNC}] \ \\ 364 \kw{READ (LUINP,*) N, THR\_VIRTUNC} \\ 365 Truncate virtual space after SCF or MCSCF, write reduced orbital information to 366 "\verb|SIRIUS.RST|" and stop \dalton. Start a new \dalton\ calculation with the 367 reduced set of molecular orbitals using ".MOSTART NEWORB" and, if MCSCF, ".STARTOLDCI" 368 in the relevant input sections (the ".RESTART" option cannot be used). 369 In input N is either 2 or 4, and all virtual orbitals with eigenvalues of 370 $r^N$ greater than ( THR\_VIRTRUNC )$^N$ are deleted. 371 The THR\_VIRTRUNC is thus a measure of the maximum extent (diffuseness) of a virtual orbital. 372 All the occupied orbitals are not modified. 373 374\item[\Key{NEVPT2}] 375 Multireference second-order perturbation theory calculation.\index{NEVPT2} 376 Requires preceding MCSCF or MC--srDFT calculation. 377 378\end{description} 379 380\end{description} 381 382{\bf Secondary keywords (in alphabetical order): } 383 384\begin{description} 385 386\item[\Key{ERF}] \ \\ 387 \kw{READ (LUINP,*) new\_mu\_value} \\ 388 Default range-separation for all srDFT modelse is the error function with $\mu = 0.4$, our standard value. 389 With this option you can change the $\mu$ as desired. 390 391\item[\Key{FLAGS}] \ \\ 392 \kw{READ (LUINP,NMLSIR)} \\ 393 Read namelist "NMLSIR". Example: \verb" $NMLSIR NPATH=3,5,-7, $END" \\ 394 Set internal flags no. 3 and 5 to true and flag no. 7 to false. 395 Only for debugging. Set internal control flags directly. 396 For example \verb" &NMLSIR NPATH=61,-43, &END" sets flag(61) true and flag(43) false. 397 Usage is not further documented. 398 399\item[\Key{INTERFACE}] 400 Write the "\verb|SIRIFC|" interface file\index{interface file} for post-processing programs. 401 402%hjaaj oct 2003: obsolete ... 403%\item[\Key{NSYM}] 404%% Required, no defaults. \\ 405% Default: specified by integral program \\ 406% \verb"READ (LUINP,*) NSYM" \\ 407% Number of spatial Abelian symmetries (1, 2, 4, or 8), corresponding 408% to $D_{2h}$ or one of its subgroups. 409 410\item[\Key{PRINT}] \ \\ 411 \kw{READ (LUINP,*) IPRSIR} \\ 412 General {\sir} print level and default for all other print parameters in this module 413 (default is the general print level from \verb|**DALTON|). 414 415\item[\Key{RESTART}] 416 Restart {\sir}\index{restart!wave function} second order optimization of HF, HF-srDFT, MCSCF, or MC--srDFT. 417 The {\sir} restart file (\verb|SIRIUS.RST|) must be available and contain restart information. 418 419%hjaaj Oct 2003: obsolete, we want the specific .HF or .DFT 420%\item[\Key{SCF}] 421% Alias for the \quotekw{\Key{HF}} keyword. 422 423\item[\Key{STOP}] \ \\ 424 \kw{READ (LUINP,'(A20)') REWORD} \\ 425 Terminate {\sir} according to the instruction given on the following line. 426 Three stop points are defined: 427\begin{enumerate} 428 429\item \hspace{2em} \quotekw{ AFTER INPUT} 430 431\item \hspace{2em} \quotekw{ AFTER MO-ORTHONORMALIZATION} 432 433\item \hspace{2em} \quotekw{ AFTER GRADIENT} (only for MCSCF and 2nd-order HF or DFT) 434\end{enumerate} 435 436\item[\Key{TITLE}] \ \\ 437 \kw{READ (LUINP,'(A)') TITLE(NTIT)} \ \\ 438 Any number of title lines (until next line beginning with a 439 \quotekw{.} or \quotekw{*} prompt). 440 Up to 6 title lines will be saved and used in the output, additional 441 lines will be discarded. 442 443\item[\Key{WESTA}] 444 Write the file "\verb|SIRIUS.STRINGINFO|" with CI string information for the WESTA post-processing program. 445 446%hjaaj Oct 2003: obsolete 447%\item[\Key{BASIS SET}] 448% Default: specified by integral program \\ 449% \verb"READ (LUINP,*) (NBAS(I), I = 1,NSYM)" \\ 450% Number of basis functions per symmetry. 451\end{description} 452 453%hj%\noindent{\bf Comments:} 454 455%\ifabacus ABACUS: 456%If the full molecular Hessian is calculated in 457%ABACUS and the number of symmetries (\verb|NSYM|) is greater than 458%one, then the MCSCF wave function will be automatically calculated 459%in determinants\index{determinants} and, if singlet, 460%\quotekw{.PLUS COMBINATIONS}). This is so because the CSFs can 461%only have one spatial symmetry, and it is generally necessary to 462%solve linear response equations of several symmetries to get the 463%full molecular Hessian. 464%\fi 465 466%hjaaj Oct 2003: obsolete 467%BASIS SET is provided such that the number of basis functions in each 468%symmetry may be specified if {\sir} is modified to interface to an 469%integral program which doesn't write this information to the integral 470%file. 471 472\pagebreak[3] 473\subsection{\label{ref-auxinp}\Sec{AUXILIARY INPUT}} 474 475{\bf Purpose:} 476 477Input which does not naturally fit into any of the other 478categories. 479 480\begin{description} 481\item[\Key{NOSUPMAT}] 482 Do not use P-SUPERMATRIX integrals, but calculate Fock matrices 483 from AO integrals (slower, but requires less disk space). The 484 default is to use the supermatrix file if it exists. See option 485 \Key{NOSUP} in Chapter~\ref{sec:herminp}. 486 487%\item[\Key{ONESUP}] 488% Use same unit for P-SUPERMATRIX\index{supermatrix} and ONE-ELECTRON 489% integrals \index{one-electron integral} 490% (LUSUPM=LUONEL, default is different units). 491\end{description} 492 493\pagebreak[3] 494\subsection{\label{ref-cicinp}\Sec{CI INPUT}} 495 496{\bf Purpose:} 497 498Options for a CI calculation. 499 500\begin{description} 501\item[\Key{CIDENSITY}] 502 Calculate CI one-electron density matrix and natural 503 orbital\index{natural orbitals!CI} 504 occupations after convergence. 505 506\item[\Key{CINO}] 507 Generate CI\index{CI}\index{Configuration Interaction} natural 508 orbitals\index{natural orbitals!CINO} for CI root 509 number \kw{ISTACI}, 510 clear the \verb|SIRIUS.RST| file and write the orbitals with label \quotekw{NEWORB }. 511 The \quotekw{\Key{STATE}} option must be specified. 512 513\item[\Key{CIROOTS}] 514 Default: One root.\\ 515 \kw{READ (LUINP,*) NROOCI} \\ 516 Converge the lowest \kw{NROOCI} CI roots\index{root!CI} to threshold. 517 518\item[\Key{DISKH2}] 519 Active two-electron MO integrals on disk (see comments below). 520 521\item[\Key{MAX ITERATIONS}] \ \\ 522 \kw{READ (LUINP,*) MXCIMA} \\ 523 Max iterations in iterative diagonalization of CI matrix (default = 25). 524 525\item[\Key{STATE}] 526 Default: not specified\\ 527 \kw{READ (LUINP,*) ISTACI} \\ 528 Alternative to \quotekw{\Key{CIROOTS}}. Converge root number \kw{ISTACI} 529 to threshold, converge all lower roots only to THQMIN 530 (from the \quotekw{\Sec{OPTIMIZATION}} input group, see 531 p.~\pageref{ref-optinp}). 532 533\item[\Key{THRESH}] 534 Default = 1.D-05\\ 535 \kw{READ (LUINP,*) THRCI} \\ 536 Threshold for CI energy gradient. The CI energy will be converged to 537 approximately the square of this number. 538 539\item[\Key{THRPWF}] 540 Default is 0.05 for electronic ground states, and 0.10 for excited states.\\ 541 \kw{READ (LUINP,*) THRPWF} \\ 542 Only CI coefficients of absolut value greater than threshold are printed 543 (PWF: print wave function). 544 545\item[\Key{WEIGHTED RESIDUALS}] 546 Use energy weighted residuals\index{residual} (see comments below). 547 548\item[\Key{ZEROELEMENTS}] 549 Zero small elements in CI trial vectors (see comments below). 550\end{description} 551 552 553\noindent{\bf Comments:} 554 555DISKH2: By default the CI module will attempt to place the two-electron 556integrals with four active indices in memory for more efficient 557calculation of CI sigma vectors, if memory is insufficient for this 558the 559integrals will automatically be placed on disk. The DISKH2 keyword 560forces the integrals always to be on disk. 561 562WEIGHTED RESIDUALS: Normally the CI states will be converged to a 563residual less than the specified threshold, and this will give 564approximately the squared number of decimal places in the energy. 565Depending on the value of the energy, the eigenvectors will be converged 566to different accuracy. If the eigenvectors are wanted with, for instance at 567least 6 decimal places for property calculations, specify a threshold of 5681.0D-6 and weighted residuals. 569 570ZEROELEMENTS: an experimental option that might save time (if the CI 571module can use sparseness) by zeroing all elements less than 1.0D-3 572times the largest element in the CI trial vector before 573orthonormalization against previous trial vectors. 574See also \quotekw{.SYM CHECK} under \quotekw{*OPTIMIZATION} 575(p.~\pageref{ref-optinp}). 576 577 578\pagebreak[3] 579\subsection{\label{ref-civinp}\Sec{CI VECTOR}} 580 581{\bf Purpose:} 582 583To obtain initial guess for CI vector(s). 584 585\begin{description} 586\item[\Key{PLUS COMBINATIONS}] 587 Use with \quotekw{\Key{STARTHDIAGONAL}} to choose plus combination 588 of degenerate diagonal elements ({\bf STRONGLY RECOMMENDED} for 589 calculation of singlet states with \quotekw{\Key{DETERMINANTS}}). 590 591\item[\Key{SELECT}] \ \\ 592 \kw{READ (LUINP,*) ICONF} \\ 593 Select CSF (or determinant if \quotekw{\Key{DETERMINANTS}}) no. 594 ICONF as start configuration.\index{configuration!start} 595 596\item[\Key{STARTHDIAGONAL}] 597 Select configurations corresponding to the lowest diagonal elements in 598 the configuration part of the Hessian (this is the default option). 599 600\item[\Key{STARTOLDCI}] 601 Start from old CI-vector stored saved on the \verb|SIRIUS.RST| file. 602 603%\ifabacus 604%\item[.ABACUS] 605% Geometry walk, use CI vector and "GEOSAVE" information saved by 606% ABACUS at previous geometry. The "GEOSAVE" information is used 607% to decide as early as possible in the wave function optimization 608% if the step should be rejected, thus saving CPU time if the step 609% is rejected. 610%\fi 611 612\end{description} 613 614\pagebreak[3] 615\subsection{\label{ref-wavinp}\Sec{CONFIGURATION INPUT}} 616 617{\bf Purpose:} 618 619To specify the configuration part in .MCSCF and .CI calculations. 620 621\begin{description} 622\item[\Key{CAS SPACE}] \ \\ 623 \kw{READ (LUINP,*) (NASH(I),I=1,NSYM)} \\ 624 CAS calculation: Active orbitals\index{active orbital} in each symmetry. 625 626\item[\Key{ELECTRONS}] 627 Required.\\ 628 \kw{READ (LUINP,*) NACTEL} \\ 629 Number of active electrons\index{active electrons} (the number of 630 electrons to be distributed in the active orbitals). 631 The total number of electrons is this number 632 plus two times the total number of inactive orbitals. 633 634\item[\Key{INACTIVE ORBITALS}] 635 Required.\\ 636 \kw{READ (LUINP,*) (NISH(I),I=1,NSYM)} \\ 637 Number of inactive orbitals\index{inactive orbital} each symmetry. 638 639\item[\Key{RAS1 ELECTRONS}] \ \\ 640 \kw{READ (LUINP,*) NEL1MN,NEL1MX} \\ 641 Minimum and maximum number of RAS1 electrons; this can alternatively 642 be specified with \quotekw{\Key{RAS1 HOLES}} 643 644\item[\Key{RAS1 HOLES}] \ \\ 645 \kw{READ (LUINP,*) NHL1MN,NHL1MX} \\ 646 Minimum and maximum number of holes\index{electron hole} in RAS1; alternative 647 to \quotekw{\Key{RAS1 ELECTRONS}} 648 649\item[\Key{RAS1 SPACE}] \ \\ 650 \kw{READ (LUINP,*) (NAS1(I),I=1,NSYM)} \\ 651 RAS calculation: RAS1 orbital space\index{RAS1 orbital space} 652 653\item[\Key{RAS2 SPACE}] \ \\ 654 \kw{READ (LUINP,*) (NAS2(I),I=1,NSYM)} \\ 655 RAS calculation: RAS2 orbital space\index{RAS2 orbital space} 656 657\item[\Key{RAS3 ELECTRONS}] \ \\ 658 \kw{READ (LUINP,*) NEL3MN, NEL3MX} \\ 659 Minimum and maximum number of RAS3 electrons 660 661\item[\Key{RAS3 SPACE}] \ \\ 662 \kw{READ (LUINP,*) (NAS3(I),I=1,NSYM)} \\ 663 RAS calculation: RAS3 orbital space\index{RAS3 orbital space} 664 665\item[\Key{SPIN MULTIPLICITY}] 666 Default is 1 for even number of electrons, 2 for odd number of electrons. \\ 667 \kw{READ (LUINP,*) ISPIN}\\ 668 For CSF basis: state spin multiplicity\index{spin multiplicity} = $2S + 1$, 669 where $S$ is the spin quantum number. \\ 670 For determinant basis this option determines the minimum spin 671 multiplicity. The $M_S$ value is determined as (ISPIN-1)/2. 672 673\item[\Key{MS2}] 674 Default is determind by \kw{.SPIN MULTIPLICITY}. \\ 675 \kw{READ (LUINP,*) MS2}\\ 676 For CSF basis: MS2 specifies non-default $2 M_S$ value to be used in the determinant expansion of the CSFs. 677 The computationally optional MS2 value for, say, triplet is zero (default), but if you want to calculate 678 spin-density you should select MS2=2.\\ 679 For determinant basis this option should never be used, if used it must give the 680 same $M_S$ value as the \kw{.SPIN MULTIPLICTY} key word. 681 682\item[\Key{SYMMETRY}] 683 Default is 1 (totally symmetric irrep).\\ 684 \kw{READ (LUINP,*) LSYM} \\ 685 Spatial symmetry\index{symmetry} of CI and/or MCSCF wave function. 686 687\end{description} 688 689\noindent{\bf Comments:} 690 691\noindent SYMMETRY Specifies total spatial symmetry of the wave 692function in $D_{2h}$ symmetry or one of its subgroups: $C_{2v}$, $C_2h$, 693$D_2$, $C_s$, $C_i$, $C_2$, $C_1$. The symmetry number of wave 694function follows MOLECULE output ordering of symmetries ($D_{2h}$ 695subgroup irreps). 696 697\noindent 698CAS and RAS\index{RASSCF}\index{CASSCF}\index{MCSCF} are exclusive and 699both cannot be specified in the same 700MCSCF or CI\index{MCSCF}\index{CI}\index{Configuration Interaction} 701calculation. One of them {\em must} be specified. 702 703\pagebreak[3] 704\subsection{\label{ref-dftinp}\Sec{DFT INPUT}} 705 706{\bf Purpose:} 707 708To specify the parameters of the DFT integration and the optional use of empirical corrections. 709 710\begin{description} 711 712\item[\Key{DFTAC}] \ \\ 713 \kw{READ (LUINP,*) RTYPE} \\ 714 \kw{READ (LUINP,*) CTYPE} \\ 715 \kw{READ (LUINP,*) DFTIPTA, DFTIPTB, DFTBR1, DFTBR2} \\ 716 Switches on the asymptotic correction of the exchange correlation potential. This correction is a pointwise manipulation of the 717 exchange--correlation potential. This implies activation of the .DFTVXC keyword in the SCF stage. RTYPE defines the 718 potential to be used to replace the asymptotic GGA potential, possible options are MULTPOLE (a simple multipole model) 719 and LB94 (the potential from the LB94 model potential~\cite{dft:lb94}). CTYPE defines how the potential of the parent 720 functional is connected to the asymptotic model, possible options are LINEAR (as used in the Tozer-Handy correction~\cite{dft:th}), 721 TANH (a modified connection by Tozer~\cite{dft:tanh}, which removes discontinuities associated with linear interpolation) and 722 GRAC (the gradient-regulated asymptotic correction of Gr\"uning \emph{et. al.}~\cite{dft:grac}). \\ 723 Four numerical input parameters are then input 724 the first two are the $\alpha$ and $\beta$ ionization potentials (either calculated or experimental). If GRAC is chosen for the 725 connection type then the last two value specify the parameters $\alpha$ and $\beta$ (see Ref.~\cite{dft:grac} for details). 726 Recommended values are 0.5 and 40.0. Otherwise the last two parameters specify multiples of the 727 Bragg Radii and are used to define the core, interpolation and asymptotic regions. For grid points within DFTBR1 Bragg Radii of 728 each atom the potential is unmodified, for points outside DFTBR2 Bragg Radii the potential is replaced with its asymptotic model. 729 In between the interpolation model is used. Recommended values in this case are 3.5 and 4.7. Care should be taken when 730 choosing alternative values for the final two parameters in each scheme, inappropriate values can make SCF convergence difficult. 731 732 733\item[\Key{DFTD2}] 734 switches on Grimme's DFT-D2 empirical dispersion correction~\cite{dft:dftd2}. 735 The code will attempt to assign the correct functional dependent 736 parameters based on the chosen DFT functional. Analytic gradient contributions are available. 737 738\item[\Key{D2PAR}] \ \\ 739 \kw{READ (LUINP,*) D2\_s6\_inp, D2\_alp\_inp, D2\_rs6\_inp} \\ 740 using this keyword user input values of the $s_6$, $\alpha$ and $s_{r,6}$ DFT-D2 parameters may be specified. If supplied these values override 741 any values defined within the code. 742 743\item[\Key{DFTD3}] 744 switches on Grimme's DFT-D3 empirical dispersion correction~\cite{dft:dftd3}. The code will attempt to assign the correct functional dependent 745 parameters based on the chosen DFT functional. Analytic gradient contributions are available. 746 747\item[\Key{DFD3BJ}] 748 switches on Grimme's DFT-D3 empirical dispersion correction with Becke-Johnson damping~\cite{dft:dftd3bj}. 749 The code will attempt to assign the correct functional dependent parameters based on the chosen DFT functional. 750 Analytic gradient contributions are available. This is the presently recommended version. 751 752\item[\Key{3BODY}] 753 keyword for adding 3-body terms to the DFT-D3 dispersion energy. Note that gradients are not implemented for these corrections 754 755\item[\Key{D3PAR}] \ \\ 756 \kw{READ (LUINP,*) D3\_s6\_inp, D3\_alp\_inp, D3\_rs6\_inp, D3\_rs18\_inp, D3\_s18\_inp} \\ 757 keyword for specifying the $s_6$, $\alpha$, $s_{r,6}$, $s_{r,8}$ and $s_8$ parameters of the DFT-D3 methods. Note, take care to 758 match the parameter values to the correct version of the DFT-D3 correction. 759 760\item[\Key{DFTELS}] \ \\ 761 \kw{READ (LUINP,*) DFTELS} \\ 762 safety threshold -- stop if the charge integration gives too large 763 error. 764 765\item[\Key{DFTTHR}] \ \\ 766 \kw{READ (LUINP,*) DFTHRO, DFTHRI} \\ 767 Thresholds determining accuracy of the numerical integration. The 768 first number determines the density threshold (contributions to a 769 property from places where the density is below the threshold will 770 be skipped) and the second one -- orbital threshold (orbitals are 771 assumed to be exactly 0 if they are below the threshold). The 772 default value for DFTHR0 is $1.0D-9$ and for DFTRHI is $1.0D-13$. 773 774\item[\Key{DFTVXC}] 775 keyword to specify explicit construction of the exchange--correlation 776 potential for GGA forms. This is automatically invoked when .DFTAC is selected 777 and not recommended for use otherwise. 778 779\item[\Key{RADINT}] \ \\ 780 \kw{READ (LUINP,*) RADINT} \\ 781 Determines the quality of the radial part of the grid and 782 corresponds to the upper limit of the error in case of an 783 integration on an atom. Default value is $1.0D-13$. 784 785\item[\Key{ANGINT}] \ \\ 786 \kw{READ (LUINP,*) ANGINT} \\ 787 Determines the quality of the angular Lebedev grid -- the angular 788 integration of spherical harmonics will be exact up to the specified 789 order. Default value is 35. 790 791\item[\Key{GRID TYPE}] \ \\ 792 \kw{READ (LUINP,*) LINE} \\ 793 Allows specification of different partitioning methods and radial 794 schemes. \verb|BECKE| is Becke partitioning scheme with correction 795 for atomic sizes using Bragg sizes, \verb|BECKEORIG| is the same 796 Becke partitioning scheme but without correction. \verb|SSF| is a 797 partitioning scheme for large molecules designed to reduce the grid 798 generation time. \verb|LMG| select LMG radial scheme adjusted to 799 currently used basis set. Gauss-Chebychev radial scheme of second 800 order is provided for reference and can be selected by keyword 801 \verb|GC2|. 802 803% The default is \verb|BECKE LMG| which is optimal for an 804% overwhelming number of cases. 805\item[\Key{COARSE}] 806 Shortcut keyword for radial integration accuracy $10^{-11}$ and 807 angular expansion order equal to $35$. 808\item[\Key{NORMAL}] 809 Default. Shortcut keyword for radial integration accuracy $10^{-13}$ and 810 angular expansion order equal to $35$. 811\item[\Key{FINE}] 812 Shortcut keyword for radial integration accuracy $10^{-13}$ and 813 angular expansion order equal to $42$. 814\item[\Key{ULTRAF}] 815 Shortcut keyword for radial integration accuracy $10^{-15}$ and 816 angular expansion order equal to $65$. 817 818\end{description} 819 820\subsection{\label{ref-dft}Kohn--Sham DFT functionals} 821 822In general, functionals in \dalton\ can be divided into two groups: 823generic exchange and correlation functionals 824and combined functionals. Combined functionals are a linear combination of 825generic ones. There are a large number of combined functionals defined below, 826however the user can also create their own combined functionals with 827the \verb|Combine| keyword. 828A number of standalone functionals are also included within \dalton. 829In addition a number of double-hybrid functionals (energies only) are available, 830which include a post-SCF second-order perturbation theory contribution. 831 832It should be noted that the input is not case sensitive, although the notation 833employed in this manual makes use of case to emphasize exchange or correlation 834functional properties and reflect the original literature sources. 835 836 837\subsubsection{Exchange Functionals} 838\providecommand\exfn[1]{#1} 839\begin{description} 840 841\item[Slater] Dirac-Slater exchange functional 842\cite{dft:hohenberg,dft:kohn,dft:slater}.\index{Slater} 843 844\item[Becke] 1988 Becke exchange GGA correction \cite{dft:becke88}. 845 Note that the full Becke88 exchange functional is given as 846 \exfn{Slater} + \exfn{Becke}.\index{Becke} 847 848\item[mBecke] 1998 modified \exfn{Becke} exchange correction presented in reference 849 \cite{dft:edf1} for use in the EDF1 functional. The $\beta$ value 850 of 0.0042 in \exfn{Becke} is changed to 0.0035.\index{mBecke}\index{EDF1} 851 852\item[B86] Becke 1986 exchange functional, a divergence free, semi-empirical 853 gradient-corrected exchange functional~\cite{dft:b86,dft:b86r}.\index{B86} This 854 functional corresponds to the B86R functional of the Molpro program. 855 856\item[B86mx] B86 exchange functional modified with a gradient correction 857 for large density gradients~\cite{dft:b86mgc}.\index{B86mx} 858 859\item[DBx] Double-Becke exchange functional defined in 1998 by 860 Gill et al.\cite{dft:edf1,dft:edf2} for use in the EDF1 functional. 861 The full DBx functional is defined as 862 863 1.030952*\exfn{Slater} - 8.44793*\exfn{Becke} + 10.4017*\exfn{mBecke} 864 \index{EDF1}\index{Double-Becke}\index{Becke} 865 866\item[DK87x] DePristo and Kress' 1987 rational function GGA exchange functional 867 (equation 7) from Ref. \cite{dft:dk87}.\index{DK87} The full exchange 868 functional is defined as \exfn{Slater} + \exfn{DK87x}. 869 870%\item[FT97ax] Filatov and Thiel 1997 (FT97) exchange functional GGA correction, 871% variant A.~\cite{dft:ft97}.\index{FT97} 872% The complete exchange functional is given by \exfn{Slater} + \exfn{FT97ax}. 873% 874%\item[FT97bx] Filatov and Thiel 1997 (FT97) exchange functional GGA correction, 875% variant B.~\cite{dft:ft97}.\index{FT97} In this variant, the $\beta$ parameter 876% is a switching function dependent on the density gradient, $\nabla n_{\sigma}$ 877% and only significantly varies from variant A calculated molecular properties 878% if core electron effects are significant. This is the default exchange functional 879% in the combined FT97 exchange-correlation functional. 880% The complete exchange functional is given by \exfn{Slater} + \exfn{FT97bx}. 881 882\item[G96x] Gill's 1996 GGA correction exchange functional~\cite{dft:g96}.\index{G96} 883 The complete exchange functional is given by \exfn{Slater} + \exfn{G96x}. 884 885\item[LG93x] 1993 GGA exchange functional~\cite{dft:lg93,dft:g961lyp}.\index{LG93} 886 The full LG93 exchange functional is given by \exfn{Slater} + \exfn{LG93x} 887 888\item[LRC95x] 1995 GGA exchange functional with correct asymptotic behavior~\cite{dft:lrc95}.\index{LRC95} 889 The LRC95x exchange functional includes the Slater exchange (Eq 6 from original reference). 890 891\item[KTx] Keal and Tozer's 2003 GGA exchange functional. Note that the gradient correction 892 pre-factor constant, $\gamma$, is not included in the KT exchange 893 definition, but rather in the KT1, KT2 and KT3 definitions. The full KT exchange is given by 894 \cite{dft:kt12}\index{KT}, 895 896 \exfn{Slater} + $\gamma$\exfn{KTx} ($\gamma$ is -0.006 for KT1,KT2 and -0.004 for KT3). 897 898\item[OPTX] Handy's 2001 exchange functional correction \cite{dft:optx}.\index{OPTX} 899 The full OPTX exchange functional is given by 900 1.05151*\exfn{Slater} - 1.43169*\exfn{OPTX}. 901 902\item[PBEx] Perdew, Burke and Ernzerhof 1996 exchange functional~\cite{dft:pbe}.\index{PBEx} 903 904\item[revPBEx] Zhang and Wang's 1998 revised PBEx exchange functional, with $\kappa$ of 1.245 905 \cite{dft:revpbe}.\index{revPBE}\index{PBE} 906 907\item[RPBEx] Hammer, Hansen and N{\o}rskov's 1999 revised PBEx exchange functional 908 \cite{dft:revpbe}.\index{RPBE}\index{PBE} 909 910\item[mPBEx] Adamo and Barone's 2002 modified PBEx exchange functional~\cite{dft:mpbe}. 911 \index{mPBE}\index{PBE} 912 913\item[PW86x] Perdew and Wang 1986 exchange functional (the PWGGA-I functional) 914 ~\cite{dft:pw86x}.\index{PW86x} 915 916\item[PW91x] Perdew and Wang 1991 exchange functional (the pwGGA-II functional) 917 and includes Slater exchange \cite{dft:pw91}.\index{PW86x} This functional is 918 also given in a separate parameterization in Refs.~\cite{dft:g96,dft:mpw}, 919 which is labeled PW91x2, and is defined as 920 \exfn{PW91x} = \exfn{Slater} + \exfn{PW91x2}. 921 922\item[mPW] Adamo and Barone's 1998 modified PW91x GGA correction exchange functional 923 ~\cite{dft:pw91,dft:mpw}. The full exchange functional is given by 924 \exfn{Slater} + \exfn{mPW}.\index{mPW} 925 926\end{description} 927 928\subsubsection{Correlation Functionals} 929\providecommand\corfn[1]{#1} 930\begin{description} 931 932\item[VWN3] correlation functional of Vosko, Wilk and Nusair, 1980 (equation III) 933 \cite{dft:vwn}. This is the form used in the Gaussian program.\index{VWN3} 934 935\item[VWN5] correlation functional of Vosko, Wilk and Nusair, 1980 (equation 936 V -- the recommended one). The VWN keyword is a synonym for VWN5~\cite{dft:vwn}.\index{VWN5} 937 938%\item[FT97c] Filatov and Thiel 1997 (FT97) correlation functional 939% \cite{dft:ft97}.\index{FT97} 940 941\item[LYP] correlation functional by Lee, Yang and Parr, 1988 942 \cite{dft:lyp1,dft:lyp2}.\index{LYP} 943 944\item[LYPr] 1998 modified \corfn{LYP} functional, which is the re-parameterized EDF1 version 945 with modified parameters (0.055, 0.158, 0.25, 0.3505) 946 \cite{dft:lyp1,dft:lyp2,dft:edf1}.\index{LYPr}\index{EDF1} 947 948\item[P86c] non-local part of the correlation functional of the Perdew 1986 correlation functional 949 \cite{dft:p86}. PZ81 (1981 Perdew local) is usually used for the local part of the 950 functional, with a total corelation functional of \index{P86}\index{PZ81} 951 \corfn{P86c} + \corfn{PZ81}. 952 953\item[PBEc] Perdew, Burke and Ernzerhof 1996 correlation functional, 954 defined as PW91c local and PBEc non-local correlation~\cite{dft:pbe}.\index{PBEc} 955 956\item[PW91c] 1991 correlation functional of Perdew and Wang (the pwGGA-II functional) 957 ~\cite{dft:pw91}.\index{PW91} This functional includes both the PW91c non-local and 958 PW91c local (ie PW92c) contributions. The non-local PW91c contribution may be determined 959 as \corfn{PW91c} - \corfn{PW92c}. 960 961\item[PW92c] local correlation functional of Perdew and Wang, 1992~\cite{dft:pw91,dft:pw92}.\index{PW91} 962 This functional is the local contribution to the PW91c correlation functional. 963 964\item[PW92ac] gradient correction to the PW91c correlation functional of Perdew and Wang, 965 equation 16 from Ref.~\cite{dft:pw91,dft:pw92}.\index{PW91} The PWGGA-IIA functional 966 as defined in the original reference is \corfn{PW91c} + \corfn{PW92ac}. 967 968\item[PZ81] local correlation functional of Perdew and Zunger, 1981~\cite{dft:pz81}.\index{PZ81} 969 970\item[Wigner] original 1938 spin-polarized correlation functional~\cite{dft:wigner}.\index{Wigner} 971 972\item[WL90c] Wilson and Levy's 1990 non-local spin-dependent correlation functional 973 (equation 15 from Ref.~\cite{dft:wl90}).\index{WL90} 974 975\end{description} 976 977\subsubsection{Standalone Functionals} 978\providecommand\onefn[1]{#1} 979\begin{description} 980 981\item[LB94] asymptotically correct functional of Leeuwen and 982 Baerends 1994~\cite{dft:lb94}. This functional improves description of the 983 asymptotic density on the expense of core and inner valence.\index{LB94} 984 985\item[B97] Becke 1997 functional~\cite{dft:b97}.\index{B97} 986 987\item[B97-1] Hamprecht et al.'s 1998 re-parameterization of the 988 B97 functional~\cite{dft:b97-1}.\index{B97}\index{B97-1} 989 990\item[B97-2] Modification of B97 functional in 2001 by Wilson, Bradley and Tozer 991 \cite{dft:b97-2}.\index{B97}\index{B97-2} 992 993\item[B97-D] Grimme's re-parameterization of the B97-1 functional for use with 994empirical dispersion correction~\cite{dft:b97-d}.\index{B97}\index{B97-D} 995 996\item[B97-K] Boese and Martin 2004 re-parameterization of the 997 B97-1 functional for kinetics~\cite{dft:b97-1}.\index{B97}\index{B97-K} 998 999\item[HCTH] is a synonym for the HCTH407 functional (detailed below). 1000 \cite{dft:hcth407}.\index{HCTH}\index{HCTH407} 1001 1002\item[1-4] The ``quarter'' functional of Menconi, Wilson and Tozer 1003 \cite{dft:14}.\index{1-4}\index{1-4} 1004 1005\item[HCTH93] Original 1998 HCTH functional, parameterized on a set of 1006 93 training systems~\cite{dft:hcth93}.\index{HCTH}\index{HCTH93} 1007 1008\item[HCTH120] The HCTH functional parameterized on a set of 120 training systems 1009 in 2000~\cite{dft:hcth120}.\index{HCTH}\index{HCTH120} 1010 1011\item[HCTH147] The HCTH functional parameterized on a set of 147 training systems 1012 in 2000~\cite{dft:hcth120}.\index{HCTH}\index{HCTH147} 1013 1014\item[HCTH407] The HCTH functional parameterized on a set of 407 training systems 1015 in 2001~\cite{dft:hcth407}.\index{HCTH}\index{HCTH407} 1016 1017\item[HCTH407p] The HCTH407 functional re-parameterized in 2003 on a set of 407 1018 training systems and ammonia dimer to incorporate hydrogen bonding 1019 \cite{dft:hcth407p}.\index{HCTH}\index{HCTH407}\index{HCTH407p} 1020 1021\end{description} 1022 1023\subsubsection{Combined functionals} 1024\providecommand\funexample[1]{\\{\tt #1 }} 1025\begin{description} 1026 1027\item[Combine] is a universal keyword allowing users to manually 1028 construct arbitrary linear combinations of exchange and correlation 1029 functionals from the list above. Even\index{Combine} fractional 1030 Hartree--Fock exchange can be specified. This keyword is to be 1031 followed by a string of functionals with associated weights. 1032 The syntax is \verb|NAME=WEIGHT ...|. 1033 As an example, B3LYP may be constructed as: 1034\begin{verbatim} 1035.DFT 1036 Combine HF=0.2 Slater=0.8 Becke=0.72 LYP=0.81 VWN=0.19 1037\end{verbatim} 1038 1039The following GGA and hybrid functional aliases are defined within 1040\dalton\ and provide further examples of the Combine keyword. 1041 1042\item[SVWN5] is a sum of Slater functional and VWN (or VWN5) correlation 1043 functional. SVWN is a synonym for SVWN5. It is equivalent to 1044 \funexample{Combine Slater=1 VWN5=1} 1045 \index{SVWN} 1046 1047\item[SVWN3] is a sum of the Slater exchange functional and VWN3 correlation 1048 functional. It is equivalent to the Gaussian program LSDA functional 1049 and can alternatively be selected by following set of keywords 1050 \funexample{Combine Slater=1 VWN3=1} 1051 \index{SVWN3} 1052 1053\item[LDA] A synonym for SVWN5 (or SVWN). \index{LDA} 1054 1055\item[BVWN] is a sum of the \exfn{Slater} functional, \exfn{Becke} correction and 1056 \corfn{VWN} correlation functional. It is equivalent to 1057 \funexample{Combine Slater=1 Becke=1 VWN=1} 1058 \index{BVWN} 1059 1060\item[BLYP] is a sum of Slater functional, Becke88 correction and LYP 1061 correlation functional. It is equivalent to 1062 \funexample{Combine Slater=1 Becke=1 LYP=1} 1063 \index{BLYP} 1064 1065\item[B3LYP] 3-parameter hybrid functional \cite{dft:b3lyp} equivalent to: 1066 \funexample{Combine HF=0.2 Slater=0.8 Becke=0.72 LYP=0.81 VWN=0.19} 1067 \index{B3LYP} 1068 1069\item[B3LYPg] hybrid functional with VWN3 form used for 1070 correlation---this is the form used by the Gaussian quantum chemistry 1071 program. Keyword B3LYPGauss is a synonym for B3LYPg.\index{B3LYPG} 1072 This functional can be explicitely set up by 1073 \funexample{Combine HF=0.2 Slater=0.8 Becke=0.72 LYP=0.81 VWN3=0.19} 1074 \index{B3LYP, Gaussian version} 1075 1076\item[B1LYP] 1-parameter hybrid functional with 25\% exact exchange \cite{dft:b1lyp}. 1077 Equivalent to: \funexample{Combine HF=0.25 Slater=0.75 Becke=0.75 LYP=1} 1078 \index{B3LYP} 1079 1080\item[BP86] Becke88 exchange functional and Perdew86 correlation 1081 functional (with Perdew81 local correlation). The explicit form is: 1082 \funexample{Combine Slater=1 Becke=1 PZ81=1 P86c=1} 1083 \index{BP86} 1084 1085\item[B3P86] variant of \verb|B3LYP| with VWN used for local 1086 correlation and P86 for the nonlocal part. 1087 \funexample{Combine HF=0.2 Slater=0.8 Becke=0.72 P86c=0.81 VWN=1} 1088 \index{B3P86} 1089 1090\item[B3P86g] variant of \verb|B3LYP| with VWN3 used for local 1091 correlation and P86 for the nonlocal part. 1092 This is the form used by the Gaussian quantum chemistry program. 1093 \funexample{Combine HF=0.2 Slater=0.8 Becke=0.72 P86c=0.81 VWN3=1} 1094 \index{B3P86}\index{B3P86, Gaussian version} 1095 1096\item[BPW91] Becke88 exchange functional and PW91 correlation 1097 functional. The explicit form is: 1098 \funexample{Combine Slater=1 Becke=1 PW91c=1} 1099 \index{BPW91} 1100 1101\item[B3PW91] 3-parameter Becke-PW91 functional, with PW91 correlation 1102 functional. Note that PW91c includes PW92c local correlation, thus only 1103 excess PW92c local correlation is required (coefficient of 0.19). 1104 \funexample{Combine HF=0.2 Slater=0.8 Becke=0.72 PW91c=0.81 PW92c=0.19} 1105 \index{B3PW91} 1106 1107\item[B1PW91] 1-parameter hybrid functional \cite{dft:b1lyp} equivalent to: 1108 \funexample{Combine HF=0.25 Slater=0.75 Becke=0.75 PW91c=1} 1109 \index{B1PW91} 1110 1111\item[B86VWN] is a sum of \exfn{Slater} and \exfn{B86x} exchange functionals and 1112 the \corfn{VWN} correlation functional. It is equivalent to 1113 \funexample{Combine Slater=1 B86x=1 VWN=1} 1114 \index{B86VWN} 1115 1116\item[B86LYP] is a sum of \exfn{Slater} and \exfn{B86x} exchange functionals and 1117 the \corfn{LYP} correlation functional. It is equivalent to 1118 \funexample{Combine Slater=1 B86x=1 LYP=1} 1119 \index{B86LYP} 1120 1121\item[B86P86] is a sum of \exfn{Slater} and \exfn{B86x} exchange functionals and 1122 the \corfn{P86c} correlation functional. It is equivalent to 1123 \funexample{Combine Slater=1 B86x=1 P86c=1} 1124 \index{B86P86} 1125 1126\item[B86PW91] is a sum of \exfn{Slater} and \exfn{B86x} exchange functionals and 1127 the \corfn{PW91c} correlation functional. It is equivalent to 1128 \funexample{Combine Slater=1 B86x=1 PW91c=1} 1129 \index{B86PW91} 1130 1131\item[BHandH] is an simple Half-and-half functional. 1132 \funexample{Combine HF=0.5 Slater=0.5 LYP=1} 1133 \index{BHandH} 1134 1135\item[BHandHLYP] is another simple Half-and-half functional. 1136 \funexample{Combine HF=0.5 Slater=0.5 Becke=0.5 LYP=1} 1137 \index{BHandH} 1138 1139\item[BW] is the sum of the Becke exchange and Wigner correlation 1140 functionals \cite{dft:wigner,dft:bw}.\index{BW} 1141 \funexample{Combine Slater=1 Becke=1 Wigner=1} 1142 1143\item[CAMB3LYP] Coulomb Attenuated Method Functional of Yanai, Tew and 1144Handy \cite{dft:camb3lyp}. This functional accepts additional arguments 1145\verb|alpha|, \verb|beta| and \verb|mu| to modify the fraction of HF 1146exchange for short-range interactions, additional fraction of HF 1147exchange for long-range interaction and the interaction switching 1148factor $\mu$. This input can be specified as follows: 1149\begin{verbatim} 1150.DFT 1151 CAMB3LYP alpha=0.190 beta=0.460 mu=0.330 1152\end{verbatim} 1153\index{CAMB3LYP} 1154 1155 1156\item[rCAMB3LYP] Revised version of the CAMB3LYP Functional \cite{dft:rcamb3lyp} 1157designed to give near piecewise linear behaviour of the energy vs. particle number. 1158This functional accepts additional arguments \verb|alpha|, \verb|beta| and \verb|mu| 1159with the same meanings and syntax as for the CAMB3LYP functional.\index{rCAMB3LYP} 1160 1161\item[DBLYP] is a sum of the Double-Becke exchange functional and 1162 the LYP correlation functional 1163 \cite{dft:becke88,dft:edf1,dft:lyp1,dft:lyp2}.\index{Double-Becke} 1164 \funexample{Combine Slater=1.030952 Becke=-8.44793 mBecke=10.4017 LYP=1} 1165 1166\item[DBP86] is the sum of the Double-Becke exchange functional and 1167 the P86 correlation functional \cite{dft:becke88,dft:edf1,dft:p86}.\index{Double-Becke} 1168 \funexample{Combine Slater=1.030952 Becke=-8.44793 mBecke=10.4017 P86c=1 PZ81=1} 1169 1170\item[DBPW91] is a sum of the Double-Becke exchange functional and 1171 the PW91 correlation functional \cite{dft:becke88,dft:edf1,dft:pw91}.\index{Double-Becke} 1172 \funexample{Combine Slater=1.030952 Becke=-8.44793 mBecke=10.4017 PW91c=1} 1173 1174\item[EDF1] is a fitted functional of Adamson, Gill and Pople \cite{dft:edf1}. 1175 It is a linear combination of the Double-Becke exchange functional and the revised LYP 1176 functional LYPr.\index{EDF1} 1177 \funexample{Combine Slater=1.030952 Becke=-8.44793 mBecke=10.4017 LYPr=1} 1178 1179\item[EDF2] is a linear combination of the Hartree--Fock exchange and the Double-Becke 1180 exchange, Slater exchange, LYP correlation, revised LYPr correlation and VWN 1181 correlation functionals \cite{dft:edf2}\index{EDF2}. 1182 \funexample{Combine HF=0.1695 Slater=0.2811 Becke=0.6227 mBecke=-0.0551 VWN=0.3029 LYP=0.5998 LYPr=-0.0053} 1183 1184\item[G96VWN] is the sum of the G96 exchange functional and the VWN 1185 correlation functional \cite{dft:g96}. 1186 \funexample{Combine Slater=1 G96x=1 VWN=1} 1187 1188\item[G96LYP] is the sum of the G96 exchange functional and the LYP 1189 correlation functional \cite{dft:g96}. 1190 \funexample{Combine Slater=1 G96x=1 LYP=1} 1191 1192\item[G96P86] is the sum of the G96 exchange functional and the P86 1193 correlation functional \cite{dft:g96}. 1194 \funexample{Combine Slater=1 G96x=1 P86c=1} 1195 1196\item[G96PW91] is the sum of the G96 exchange functional and the PW91 1197 correlation functional \cite{dft:g96}. 1198 \funexample{Combine Slater=1 G96x=1 PW91c=1} 1199 1200\item[G961LYP] is a 1-parameter B1LYP type functional with the exchange gradient 1201 correction provided by the G96x functional \cite{dft:g961lyp}. 1202 \funexample{Combine HF=0.25 Slater=0.75 G96x=0.75 LYP=1} 1203 1204\item[KMLYP] Kang and Musgrave 2-parameter hybrid functional with a mixture of 1205 Slater and Hartree--Fock exchange and VWN and LYP correlation functionals. 1206 \cite{dft:kmlyp}. 1207 \funexample{Combine HF=0.557 Slater=0.443 VWN=0.552 LYP=0.448} 1208 1209\item[KT1] Slater-VWN5 functional with the KT GGA exchange correction 1210 \cite{dft:kt12,dft:kt12a}.\index{KT1} 1211 \funexample{Combine Slater=1 VWN=1 KT=-0.006} 1212 1213\item[KT2] differs from KT1 only in that the weights of the Slater and 1214 VWN5 functionals are from an empirical fit (not equal to 1.0) 1215 \cite{dft:kt12,dft:kt12a}.\index{KT2} 1216 \funexample{Combine Slater=1.07173 VWN=0.576727 KT=-0.006} 1217 1218\item[KT3] a hybrid functional of Slater, OPTX and KT exchange with the 1219 LYP correlation functional \cite{dft:kt3}. The explicit form is 1220 \funexample{Combine Slater=1.092 KT=-0.004 LYP=0.864409 OPTX=-0.925452} 1221 \index{KT3} 1222 1223\item[LG1LYP] is a 1-parameter B1LYP type functional with the exchange gradient 1224 correction provided by the LG93x functional \cite{dft:g961lyp}. 1225 \funexample{Combine HF=0.25 Slater=0.75 LG93x=0.75 LYP=1} 1226 1227\item[mPWVWN] is the combination of mPW exchange and VWN correlation functionals 1228 \cite{dft:mpw,dft:vwn}.\index{mPWVWN} 1229 \funexample{Combine Slater=1 mPW=1 VWN=1}. 1230 1231\item[mPWLYP] is the combination of mPW exchange and LYP correlation functionals 1232 \cite{dft:mpw,dft:vwn}.\index{mPWLYP} 1233 \funexample{Combine Slater=1 mPW=1 LYP=1}. 1234 1235\item[mPWP86] is the combination of mPW exchange and P86 correlation functionals 1236 \cite{dft:mpw,dft:vwn}.\index{mPWP86} 1237 \funexample{Combine Slater=1 mPW=1 P86c=1 PZ81=1}. 1238 1239\item[mPWPW91] is the combination of mPW exchange and PW91 correlation functionals 1240 \cite{dft:mpw,dft:pw91}.\index{mPWPW91} 1241 \funexample{Combine Slater=1 mPW=1 PW91c=1}. 1242 1243\item[mPW3PW91] is a 3-parameter combination of mPW exchange and PW91 correlation 1244 functionals, with the PW91 (PW92c) local correlation~\cite{dft:mpw}.\index{mPW3PW91} 1245 \funexample{Combine HF=0.2 Slater=0.8 mPW=0.72 PW91c=0.81 PW92c=0.19}. 1246 1247\item[mPW1PW91] is a 1-parameter combination mPW exchange and PW91 correlation 1248 functionals with 25\% Hartree--Fock exchange \cite{dft:mpw}.\index{mPW1PW91} 1249 \funexample{Combine HF=0.25 Slater=0.75 mPW=0.75 PW91c=1}. 1250 1251\item[mPW1K] optimizes mPW1PW91 for kinetics of H abstractions, with 42.8\% Hartree--Fock 1252 exchange \cite{dft:mpw1k}.\index{mPW1PW91} 1253 \funexample{Combine HF=0.428 Slater=0.572 mPW=0.572 PW91c=1}. 1254 1255\item[mPW1N] optimizes mPW1PW91 for kinetics of H abstractions, with 40.6\% Hartree--Fock 1256 exchange \cite{dft:mpw1n}.\index{mPW1N} 1257 \funexample{Combine HF=0.406 Slater=0.594 mPW=0.594 PW91c=1}. 1258 1259\item[mPW1S] optimizes mPW1PW91 for kinetics of H abstractions, with 6\% Hartree--Fock 1260 exchange \cite{dft:mpw1s}.\index{mPW1S} 1261 \funexample{Combine HF=0.06 Slater=0.94 mPW=0.94 PW91c=1}. 1262 1263\item[OLYP] is the sum of the OPTX exchange functional with the 1264 LYP correlation functional \cite{dft:optx,dft:lyp1,dft:lyp2}. 1265 \funexample{Combine Slater=1.05151 OPTX=-1.43169 LYP=1} 1266 \index{OLYP} 1267 1268\item[OP86] is the sum of the OPTX exchange functional with the 1269 P86 correlation functional \cite{dft:optx,dft:p86}. 1270 \funexample{Combine Slater=1.05151 OPTX=-1.43169 P86c=1 PZ81=1} 1271 \index{OP86} 1272 1273\item[OPW91] is the sum of the OPTX exchange functional with the 1274 PW91 correlation functional \cite{dft:optx,dft:pw91}. 1275 \funexample{Combine Slater=1.05151 OPTX=-1.43169 PW91c=1} 1276 \index{OPW91} 1277 1278\item[PBE0] a hybrid functional of Perdew, Burke and Ernzerhof with 1279 0.25 weight of exact exchange, 0.75 of \verb|PBEx| exchange functional and 1280 the \verb|PBEc| correlation functional \cite{dft:pbe0}. 1281 Alternative aliases are PBE1PBE or PBE0PBE.\index{PBE0} 1282 \funexample{Combine HF=0.25 PBEx=0.75 PBEc=1} 1283 1284\item[PBE] same as above but with exchange estimated exclusively by 1285 \exfn{PBEx} functional \cite{dft:pbe}.\index{PBE} Alias: PBEPBE. 1286 \funexample{Combine PBEx=1 PBEc=1} 1287 1288\item[RPBE] is a revised PBE functional that employs the 1289 \exfn{RPBEx} exchange functional. 1290 \funexample{Combine RPBEx=1 PBEc=1} 1291 1292\item[revPBE] is a revised PBE functional that employs the 1293 \exfn{revPBEx} exchange functional. 1294 \funexample{Combine revPBEx=1 PBEc=1} 1295 1296\item[mPBE] is a revised PBE functional that employs the 1297 \exfn{mPBEx} exchange functional. 1298 \funexample{Combine mPBEx=1 PBEc=1} 1299 1300\item[PW91VWN] is the combination of PW91 exchange and VWN correlation functionals 1301 \cite{dft:pw91,dft:vwn}.\index{PW91} 1302 \funexample{Combine PW91x=1 VWN=1}. 1303 1304\item[PW91LYP] is the combination of PW91 exchange and LYP correlation functionals 1305 \cite{dft:pw91,dft:lyp1,dft:lyp2}.\index{PW91} 1306 \funexample{Combine PW91x=1 LYP=1}. 1307 1308\item[PW91P86] is the combination of PW91 exchange and P86 (with Perdew 1981 local) 1309 correlation functionals \cite{dft:pw91,dft:pw86,dft:pz81}. 1310 \funexample{Combine PW91x=1 P86c=1 PZ81=1}. 1311 1312\item[PW91PW91] is the combination of PW91 exchange and PW91 correlation functionals. 1313 Equivalent to PW91 keyword \cite{dft:pw91}. 1314 \funexample{Combine PW91x=1 PW91c=1}. 1315 1316\item[XLYP] is a linear combination of \exfn{Slater}, \exfn{Becke} and \exfn{PW91x} 1317 exchange and \corfn{LYP} correlation functionals \cite{dft:xlyp,dft:x3lyp}.\index{XLYP} 1318 \funexample{Combine Slater=1 Becke=0.722 PW91x=0.347 LYP=1}. 1319 1320\item[X3LYP] is a linear combination of Hartree--Fock, \exfn{Slater}, \exfn{Becke} 1321 and \exfn{PW91x} exchange and \corfn{VWN} and \corfn{LYP} correlation functionals 1322 \cite{dft:xlyp,dft:x3lyp}.\index{X3LYP} 1323 \funexample{Combine HF=0.218 Slater=0.782 Becke=0.542 PW91x=0.167 VWN=0.129 LYP=0.871} 1324 1325\end{description} 1326 1327 1328Note that combinations of local and non-local correlation functionals 1329can also be generated with the Combine keyword. For example, 1330\verb|Combine P86c=1 PZ81=1| combines the PZ81 local and P86c non-local 1331correlation functional, whereas \verb|Combine VWN=1 P86c=1| 1332combines the VWN local and P86 non-local correlation functionals. 1333 1334 1335Linear combinations of all exchange and correlation functionals listed above 1336are possible with the \verb|Combine| keyword. 1337 1338\subsubsection{Double-hybrid functionals} 1339\begin{description} 1340\item[B2PLYP] is the double hybrid of Ref.~\cite{dft:b2plyp} 1341 1342\item[B2TPLYP] is a modification of the B2PLYP functional for thermodynamics~\cite{dft:b2tplyp} 1343 1344\item[mPW2PLYP] a double hybrid using an alternative GGA exchange contribution and tested on the G3/05 benchmark dataset~\cite{dft:mpw2plyp} 1345 1346\item[B2GPLYP] is a modification of the B2PLYP functional for general purpose calculations~\cite{dft:b2tplyp} 1347 1348\item[B2PIPLYP] is a form related to B2PLYP but designed to give better performance for sterically crowed or stacked aromatic ring systems~\cite{dft:b2piplyp} 1349 1350\item[PBE0DH] a theoretically derived double-hybrid parameterization~\cite{dft:pbe0dh} 1351 1352\end{description} 1353 1354Note that at present double-hybrid functionals are implemented for energies only, analytic gradient contributions are not implemented. 1355\pagebreak[3] 1356 1357\subsection{\label{ref-srdft}Short-range srDFT functionals} 1358 1359In this sections available srDFT functionals are listed. 1360Note that these functionals may only be specified if one of the 1361srDFT wave functions have been selected. 1362The functonals are actived by specifying them in the input line following the \quotekw{.SRFUN} keyword. 1363The most common srDFT functionals can be specified as a single word, whereas custom combinations of exchange and correlation are specified with two words. 1364The exchange functional must be specified first and the correlation functional second. 1365For example, \verb| SRXPBEGWS SRCPBEGWS| (which is the same combined functional as obtained with the \verb| SRPBEGWS| keyword). 1366 1367\subsubsection{Combined functionals} 1368\providecommand\onefn[1]{#1} 1369\begin{description} 1370 1371\item[SRLDA] combination of \quotekw{SRXLDA} for exchange and \quotekw{SRCVWN5} for correlation~\cite{srdft:LDAERF} 1372 1373\item[LRCLDA] combination of \quotekw{SRXLDA} for exchange and \quotekw{CVWN5} for correlation~\cite{srdft:LDAERF} 1374 1375\item[SRPBEGWS] combination of \quotekw{SRXPBEGWS} for exchange and \quotekw{SRCPBEGWS} for correlation~\cite{srdft:PBEGWSa,srdft:PBEGWSb} 1376 1377\item[LRCPBEGWS] combination of \quotekw{SRXPBEGWS} for exchange and \quotekw{CPBE} for correlation~\cite{srdft:PBEGWSa,srdft:PBEGWSb} 1378 1379\item[SRPBE0GWS] combination of \quotekw{SRXPBEGWS} with \quotekw{.HFXFAC} set to 0.25 for exchange and \quotekw{SRCPBEGWS} for correlation~\cite{srdft:PBEGWSa,srdft:PBEGWSb} 1380 1381\item[SRPBERI] combination of \quotekw{SRXPBEHSE} for exchange and \quotekw{SRCPBERI} for correlation~\cite{srdft:erfgau,srdft:Heyd2004} 1382 1383\end{description} 1384 1385\subsubsection{Exchange Functionals} 1386\providecommand\exfn[1]{#1} 1387\begin{description} 1388 1389\item[NULL] no exchange functional. 1390 1391\item[HFEXCH] 100\% full-range Hartree-Fock like exchange. Combination of HF-like exchange together with an srDFT exchange functional can be obtained with the keyword \quotekw{.HFXFAC}. 1392 1393\item[SRXLDA] a short-range LDA exchange functional based on the uniform electron gas by Paziani \textit{et al.}~\cite{srdft:LDAERF} 1394 1395\item[SRXPBEGWS] short-range GGA exchange functional based on the PBE exchange functional by Goll, Werner and Stoll~\cite{srdft:PBEGWSa,srdft:PBEGWSb} 1396 1397\item[SRXPBEHSE] short-range GGA exchange functional based on the PBE exchange functional by Heyd and Scuseria~\cite{srdft:Heyd2004} 1398 1399\end{description} 1400 1401\subsubsection{Correlation Functionals} 1402\providecommand\corfn[1]{#1} 1403\begin{description} 1404 1405\item[NULL] no correlation functional. 1406 1407\item[SRCVWN5] short-range LDA correlation functional based on VWN5 by Paziani \textit{et al.}~\cite{srdft:LDAERF} 1408 1409\item[CVWN5] full-range LDA correlation functional by Vosko, Wilk and Nusair\cite{dft:vwn} 1410 1411\item[SRCPW92] short-range LDA correlation functional based on PW92 by Paziani \textit{et al.}~\cite{srdft:LDAERF} 1412 1413\item[CPW92] full-range LDA correlation functional by Perdew and Wang, 1992~\cite{dft:pw91,dft:pw92} 1414 1415\item[SRCPBEGWS] short-range GGA correlation functional based on the PBE correlation functional by Goll, Werner and Stoll~\cite{srdft:PBEGWSa,srdft:PBEGWSb} 1416 1417\item[SRCPBERI] short-range GGA correlation functional based on rational interpolation of the PBE correlation functionalbetween the short-range limit and the long-range limit by Toulouse, Colonna and Savin~\cite{srdft:erfgau} 1418 1419\item[CPBE] full-range GGA correlation functional by Perdew, Burke and Ernzerhof~\cite{dft:pbe} 1420 1421\end{description} 1422 1423\subsubsection{Third Options} 1424\providecommand\corfn[1]{#1} 1425\begin{description} 1426 1427\item[NO\_SPINDENSITY] can be put as a third option in the functional specification to force the program to not use spin-densities. This option only works with explicitly specified exchange and correlation functional. For example, \verb|SRXPBEGWS SRCPBEGWS NO_SPINDENSITY| 1428 1429\end{description} 1430\pagebreak[3] 1431 1432\subsection{\label{ref-haminp}\Sec{HAMILTONIAN}} 1433 1434{\bf Purpose:} 1435 1436Add extra terms to the Hamiltonian (for finite field\index{finite field} calculations). 1437 1438\begin{description} 1439\item[\Key{FIELD TERM}] 1440 Default = no finite external fields added. \\ 1441 \kw{READ (LUINP, * ) EFIELD(NFIELD)} \\ 1442 \kw{READ (LUINP,'(A)') LFIELD(NFIELD)} \\ 1443 Enter field strength (in atomic units) and property label on separate lines 1444 where label is a \molecule-style property label on the file \verb|AOPROPER| 1445 produced by the property module, see Chapter~\ref{ch:hermit}. 1446 The calculation of the necessary property integral(s) must be requested 1447 in the \quotekw{**INTEGRALS} input module. \\ 1448 NOTE: Only real (symmetric) operators are allowed, becaus the wave-function 1449 choices are only implemented for real wave functions. \\ 1450 NOTE: This keyword may be repeated several times for adding more than 1451 one finite field (max \mxfelt fields). Example, to specify $\oper{H}' = 0.1 \oper{x} + 0.2 \oper{y}$: 1452 1453\begin{inputex} \begin{verbatim} 1454.FIELD TERM 1455 0.1 1456 XDIPLEN 1457.FIELD TERM 1458 0.2 1459 YDIPLEN 1460\end{verbatim} \end{inputex} 1461 1462\item[\Key{PRINT}] 1463 Default = 0.\\ 1464 \kw{READ (LUINP,*) IPRH1} \\ 1465 If greater than zero: 1466 print the one-electron Hamiltonian matrix, including 1467 specified field-dependent terms, in AO basis. 1468\end{description} 1469 1470\pagebreak[3] 1471\subsection{\label{ref-mp2inp}\Sec{MP2 INPUT}} 1472 1473{\bf Purpose:} 1474 1475\index{MP2}\index{M{\o}ller-Plesset!second-order} 1476To direct MP2 calculation. Note that MP2 energies as well as 1477properties also are available through the coupled cluster module, see 1478Chapter~\ref{ch:CC}. 1479For open--shell SCF, the singly occupied orbitals are frozen in the MP2 section. 1480 1481\begin{description} 1482 1483\item[\Key{MP2 FROZEN}] 1484 Default = no frozen orbitals\\ 1485 \kw{READ (LUINP,*) (NFRMP2(I),I=1,NSYM)} \\ 1486 Occupied SCF orbitals frozen in MP2 calculation. 1487 1488\item[\Key{PRINT}] \ \\ 1489 \kw{READ (LUINP,*) IPRMP2} \\ 1490 Print level for MP2 calculation 1491 (default is the general print level from \verb|**DALTON| plus four). 1492 1493\item[\Key{SAVE WF1}] \ \\ 1494 Save first order wave function on SIRIFC. 1495 Default is only to save first order wave function if MP2 is the last wave function level 1496 \emph{and} at least one of the modules PROPERTIES (ABACUS) or RESPONSE have been 1497 requested (presumably then for a SOPPA calculation). 1498 1499\end{description} 1500 1501\subsubsection*{Modifications of MP2 model.} 1502 1503\begin{description} 1504 1505\item[\Key{SCSMP2}] 1506 Grimme's spin-component scaled MP2 ($p_S = 1.2$, $p_T = 1/3$) 1507 1508\item[\Key{SOSMP2}] 1509 Head-Gordon's scaled opposite spin MP2 ($p_S = 1.3$, $p_T = 0$) 1510 1511\item[\Key{MP2 SCALED}] \ \\ 1512 \kw{READ (LUINP,*) p\_S, p\_T} \\ 1513 Your own scaling factors for a scaled MP2 model. 1514 1515\item[\Key{LEVELSHIFT}] \ \\ 1516 \kw{READ (LUINP,*) MP2\_LSHIFT} \\ 1517 Level shift of MP2 denominators. 1518\end{description} 1519 1520\noindent{\bf Comments:} 1521 1522The MP2 module expects canonical Hartree--Fock orbitals. The MP2 module will 1523check the orbitals and it exits if the Fock matrix has off-diagonal non-negligible 1524elements. 1525If starting from saved canonical Hartree--Fock orbitals from a previous calculations, 1526although no Hartree--Fock calculation will be done 1527the number of occupied Hartree--Fock orbitals in each symmetry must anyway be 1528specified with the \quotekw{.DOUBLY OCCUPIED} under \quotekw{*SCF INPUT}. 1529 1530The MP2 calculation will produce the MP2 energy and the natural orbitals 1531{natural orbitals!MP2} 1532for the density matrix through second order. The primary purpose of 1533this option is to generate good starting orbitals for CI or MCSCF wave 1534functions, but it 1535may of course also be used to obtain the MP2 energy, perhaps with frozen 1536core orbitals. {\em For valence MCSCF calculations it is recommended that the 1537\quotekw{\Key{MP2 FROZEN}} option is used in order to obtain the appropriate 1538correlating orbitals\index{correlating orbitals}\index{MCSCF} as start 1539for an MCSCF calculation.\/} As the commonly 1540used basis sets do not contain correlating orbitals for the core 1541orbitals and as the core correlation energy therefore becomes arbitrary, 1542the \quotekw{\Key{MP2 FROZEN}} option can also be of benefit in MP2 energy 1543calculations. 1544 1545\pagebreak[3] 1546\subsection{\label{ref-nevpt2inp}\Sec{NEVPT2 INPUT}} 1547 1548{\bf Purpose:} 1549 1550\index{NEVPT2}\index{multireference PT!second-order} 1551Calculation of the second order correction to the energy for a 1552CAS--SCF or CAS--CI zero order wavefunction. 1553The user is referred to Chapter~\ref{ch:nevpt2} on 1554page~\pageref{ch:nevpt2} for a brief 1555introduction to the $n$--electron valence state second order 1556perturbation theory (NEVPT2). 1557 1558\begin{description} 1559\item[\Key{THRESH}] 1560 Default = 0.0\\ 1561 \kw{READ (LUINP,*) THRNEVPT} \\ 1562 Threshold to discard small coefficients in the CAS wavefunction 1563 1564\item[\Key{FROZEN}] 1565 Default = no frozen orbitals\\ 1566 \kw{READ (LUINP,*) (NFRNEVPT2(I),I=1,NSYM)} \\ 1567 Orbitals frozen in NEVPT2 calculation 1568 1569\item[\Key{STATE}] 1570 No default provided\\ 1571\kw{READ (LUINP,*) ISTNEVCI} \\ 1572Root number in a CASCI calculation. This keyword is unnecessary 1573(ignored) in the CASSCF case. 1574\end{description} 1575 1576 1577\noindent{\bf Comments:} 1578 1579 1580%The present version of the NEVPT2 module requires the 1581%\quotekw{\Key{DETERMINANTS}} option to be set. 1582 1583The use of canonical orbitals for the core and virtual orbitals is 1584strongly recommended since this choice guarantees compliance of the 1585results with a totally invariant form of NEVPT2 (see page~\pageref{ch:nevpt2}). 1586 1587At present the NEVPT2 module can deal with active spaces of dimension 1588not higher than 14. 1589 1590\pagebreak[3] 1591\subsection{\label{ref-optinp}\Sec{OPTIMIZATION}} 1592 1593{\bf Purpose:} 1594 1595To change defaults for optimization of an MCSCF\index{MCSCF} wave function, 1596to specify which state to converge to (lowest state or higher state in specified symmetry), 1597to invoke use of super symmetry\index{super symmetry}, 1598and to specify CORE HOLE calculations.\\ 1599Some of the options also affect a QC-HF optimization. 1600 1601\begin{description} 1602\item[\Key{ABSORPTION}] \ \\ 1603 \kw{READ (LUINP,'(A8)') RWORD} \\ 1604 RWORD = ` LEVEL 1', ` LEVEL 2', or ` LEVEL 3'\\ 1605 Orbital absorption\index{orbital absorption} in MCSCF optimization 1606 at level 1, 2, or 3, as specified 1607 (normally level 3, see comments below). This keyword may be repeated to 1608 specify more than one absorption level, the program will then begin with 1609 the lowest level requested and, when that level is converged, 1610 disable the lower level and shift to the next level. 1611% 940816-hjaaj: The following may not be true for RAS ???? 1612% Absorption at several levels are only useful in 1613% first macro iteration, therefore the lower levels are disabled after 1614% convergence. 1615 1616\item[\Key{ACTROT}] 1617 include specified active-active rotations 1618\begin{verbatim} 1619 READ (LUINP,*) NWOPT 1620 DO I = 1,NWOPT 1621 READ (LUINP,*) JWOP(1,I),JWOP(2,I) 1622 END DO 1623\end{verbatim} 1624 JWOP(1:2,I) denotes normal molecular orbital numbers (not the active 1625 orbital numbers). 1626 1627\item[\Key{ALWAYS ABSORPTION}] 1628 Absorption\index{orbital absorption} in all MCSCF macro iterations 1629 (default is to disable absorption in 1630 local region or after \quotekw{\Key{MAXABS}} macro iterations, whichever comes first). 1631 Absorption is always disabled after Newton-Raphson algorithm has been used, 1632 and thus also when doing \quotekw{\Key{CORERELAX}}, 1633 because absorption may cause variational collapse if the desired state is excited. 1634 1635\item[\Key{CI PHP MATRIX}] 1636 Default : MAXPHP = 1 (Davidson's algorithm)\\ 1637 \kw{READ (LUINP,*) MAXPHP} \\ 1638 PHP is a subblock of the CI matrix which is calculated explicitly 1639 in order to obtain improved CI trial vectors compared to the 1640 straight Davidson\index{Davidson algorithm} algorithm. The 1641 configurations corresponding to 1642 the lowest diagonal elements are selected, unless 1643 \quotekw{\Key{PHPRESIDUAL}} is specified. 1644 \kw{MAXPHP} is the maximum dimension of PHP, the actual dimension 1645 will be less if \kw{MAXPHP} will split degenerate configurations. 1646 1647\item[\Key{COREHOLE}] \ \\ 1648 \kw{READ (LUINP,*) JCHSYM,JCHORB} \\ 1649 JCHSYM = symmetry of core orbital\\ 1650 JCHORB = the orbital in symmetry JCHSYM with a single core hole\\ 1651 Single core hole\index{core hole} MCSCF calculation. The calculation must be of RAS type 1652 with only the single core-hole orbital in RAS1, the state specified with 1653 \quotekw{\Key{STATE}} is optimized with the core-hole orbital 1654 frozen\index{frozen core hole}. 1655 The specified core hole orbital must be either inactive or 1656 the one RAS1 orbital, if it is inactive then it will switch places with 1657 the RAS1 orbital and it will not be possible to also 1658 specify \quotekw{\Key{REORDER}}. If explicit reordering is required you must reorder 1659 the core orbital yourself and let \kw{JCHORB} point to the one RAS1 orbital. 1660 Orbital absorption is activated at level 2. See comments below for more information. 1661 1662\item[\Key{CORERELAX}] 1663 (ignored if \quotekw{\Key{COREHOLE}} isn't also specified)\\ 1664 Optimize state with relaxed core orbital\index{relaxed core hole} (using Newton-Raphson algorithm, 1665 it is not necessary to explicitly specify \quotekw{\Key{NR ALWAYS}}). 1666 It is assumed that this calculation follows an optimization 1667 with frozen core orbital and that the orbital has already been 1668 moved to the RAS1 space ({\it i.e.\/}, the specific value of 1669 \quotekw{JCHORB} under \quotekw{\Key{COREHOLE}} is ignored). Any 1670 orbital absorption will be ignored. 1671 1672\item[\Key{DETERMINANTS}] 1673 Use determinant\index{determinants} basis instead of CSF basis (see comments). 1674 1675\item[\Key{EXACTDIAGONAL}] 1676 Default for RAS calculations.\\ 1677 Use the exact orbital Hessian\index{orbital Hessian} diagonal. 1678 1679\item[\Key{FOCKDIAGONAL}] 1680 Default for CAS calculations.\\ 1681 Use an approximate orbital Hessian diagonal which only uses Fock 1682 contributions. 1683 1684\item[\Key{FOCKONLY}] 1685 Activate TRACI option (default : program decides).\\ 1686 Modified TRACI option where all orbitals, also active orbitals, are 1687 transformed to Fock type orbitals in each iteration. 1688 1689\item[\Key{FROZEN CORE ORBITALS}] \ \\ 1690 \kw{READ (LUINP,*) (NFRO(I),I=1,NSYM)} \\ 1691 Frozen orbitals : Number of inactive (doubly occupied) orbitals to be frozen 1692 in each symmetry (the first NFRO(I) in symmetry I) in MCSCF.\index{frozen orbitals!MCSCF} 1693 Active orbitals and specific inactive orbitals can be frozen with \quotekw{.FREEZE} 1694 under \Sec{ORBITAL INPUT}. 1695 Frozen orbitals in SCF are specified in the \Sec{SCF INPUT} input module. 1696 1697\item[\Key{MAX CI}] \ \\ 1698 \kw{READ (LUINP,*) MAXCIT} \\ 1699 maximum number of CI iterations before MCSCF (default = 3). 1700 1701\item[\Key{MAX MACRO ITERATIONS}] \ \\ 1702 \kw{READ (LUINP,*) MAXMAC} \\ 1703 maximum number of macro iterations in MCSCF optimization (default = 25). 1704\index{iteration number!MCSCF macro, max} 1705 1706\item[\Key{MAX MICRO ITERATIONS}] \ \\ 1707 \kw{READ (LUINP,*) MAXJT} \\ 1708 maximum number of micro iterations per macro iteration in MCSCF optimization 1709 (default = 24). 1710 1711\item[\Key{MAXABS}] \ \\ 1712 \kw{READ (LUINP,*) MAXABS} \\ 1713 maximum number of macro iterations with 1714 absorption\index{orbital absorption} (default = 3). 1715 1716\item[\Key{MAXAPM}] \ \\ 1717 \kw{READ (LUINP,*) MAXAPM} \\ 1718 maximum number orbital absorptions\index{orbital absorption} within 1719 a macro iteration 1720 (APM : Absorptions Per Macro iteration; default = 5) 1721 1722\item[\Key{NATONLY}] 1723 Activate TRACI option (default : program decides).\\ 1724 Modified TRACI option where the inactive and secondary orbitals are not 1725 touched (these two types of orbitals are already natural orbitals). 1726 1727\item[\Key{NEO ALWAYS}] 1728 Always norm-extended optimization (never switch to New\-ton-Raph\-son). 1729 Note: \quotekw{\Key{NR ALWAYS}} and \quotekw{\Key{CORERELAX}} 1730 takes precedence over \quotekw{\Key{NEO ALWAYS}}. 1731 1732\item[\Key{NO ABSORPTION}] 1733 Never orbital absorption\index{orbital absorption} (default settings removed) 1734 1735\item[\Key{NO ACTIVE-ACTIVE ROTATIONS}] 1736 No active-active rotations in RAS optimization. 1737 1738\item[\Key{NOTRACI}] 1739 Disable TRACI option (default : program decides). 1740 1741\item[\Key{NR ALWAYS}] 1742 Always Newton-Raphson optimization (never NEO optimization). 1743 Note: \quotekw{\Key{NR ALWAYS}} takes precedence over 1744 \quotekw{\Key{NEO ALWAYS}}. 1745 1746\item[\Key{OLSEN}] 1747 Use Jeppe Olsen's generalization of the Davidson 1748 algorithm\index{Davidson algorithm}. 1749 1750\item[\Key{OPTIMAL ORBITAL TRIAL VECTORS}] 1751 Generate "optimal" orbital trial 1752 vectors~\cite{hjajpjhajcp87}.\index{optimal orbital trial vector} 1753 1754\item[\Key{ORB\_TRIAL VECTORS}] 1755 Use also orbital trial vectors as start vectors for auxiliary roots 1756 in each macro iteration (CI trial vectors are always generated). 1757 1758\item[\Key{PHPRESIDUAL}] 1759 Select configurations for PHP matrix based on largest residual 1760 rather than lowest diagonal elements. 1761 1762\item[\Key{SIMULTANEOUS ROOTS}] 1763 Default : NROOTS = ISTATE, LROOTS = NROOTS\\ 1764 \kw{READ (LUINP,*) NROOTS, LROOTS} \\ 1765 NROOTS = Number of simultaneous roots in NEO\\ 1766 LROOTS = Number of simultaneous roots in NEO at start 1767 1768\item[\Key{STATE}] 1769 Default = 1\\ 1770 \kw{READ (LUINP,*) ISTATE} \\ 1771 Index of MCSCF Hessian\index{MCSCF Hessian} at convergence (1 for 1772 lowest state, 2 for first 1773 excited state, etc. within the spatial symmetry\index{symmetry} and 1774 spin symmetry\index{spin symmetry} 1775 specified under \Sec{CONFIGURATION INPUT}). 1776 1777\item[\Key{SUPSYM}] 1778 Enforce automatic identification of "super symmetry" 1779 \index{super symmetry} (see comments and .THRSSY keyword below).\\ 1780 Default is that "super symmetry" is not identified. 1781 1782\item[\Key{SYM CHECK}] 1783 Default: ICHECK = 2 when NROOTS $>$ 1, else ICHECK = -1.\\ 1784 \kw{READ (LUINP,*) ICHECK} \\ 1785 Check symmetry of the LROOTS start CI-vectors and remove those which 1786 have wrong symmetry ({\it e.g.\/} vectors of delta symmetry in a sigma 1787 symmetry calculation). 1788\begin{verbatim} 1789 ICHECK < 0 : No symmetry check. 1790 ICHECK = 1 : Remove those vectors which do not have the same 1791 symmetry as the ISTATE vector, reassign ISTATE. 1792 ICHECK = 2 : Remove those vectors which do not have the same 1793 symmetry as the lowest state vector before selecting 1794 the ISTATE vector. 1795 other values: check symmetry, do not remove any CI vectors. 1796\end{verbatim} 1797 The \quotekw{\Key{SIMULTANEOUS ROOTS}} input will automatically be 1798 updated if CI vectors are removed. 1799 1800\item[\Key{THRCGR}] \ \\ 1801 \kw{READ (LUINP,*) THRCGR} \\ 1802 Threshold for print of CI gradient. Default is 0.1D0. 1803 1804\item[\Key{THRESH}] 1805 Default = 1.0D-05\\ 1806 \kw{READ (LUINP,*) THRMC} \\ 1807 Convergence threshold for energy gradient in MCSCF optimization. 1808 The convergence of the energy will be approximately the square of this 1809 number. 1810 1811\item[\Key{THRSSY}] \ \\ 1812 \kw{READ (LUINP,*) THRSSY} \\ 1813 Threshold for identification of "super 1814 symmetry"\index{super symmetry} and degeneracies among 1815 "super symmetries" from matrix elements of the kinetic energy matrix 1816 (default: 5.0D-8). 1817 1818\item[\Key{TRACI}] 1819 Activate TRACI option (default : program decides).\\ 1820 Active orbitals are transformed to natural orbitals and the CI-vectors 1821 are counter-rotated such that the CI states do not change. The 1822 inactive and secondary orbitals are transformed to Fock type orbitals 1823 (corresponding to canonical orbitals for closed shell Hartree--Fock). 1824 For RAS wave functions the active orbitals are only transformed 1825 within their own class (RAS1, RAS2, or RAS3) as the wave function is 1826 not invariant to orbital rotations between the classes. For RAS, the 1827 orbitals are thus not true natural orbitals, the density matrix is 1828 only block diagonalized. Use \quotekw{\Key{IPRCNO}} (see 1829 p.~\pageref{ref-priinp}) to control output from this 1830 transformation. 1831 1832\end{description} 1833 1834 1835\noindent{\bf Comments:} 1836 1837COREHOLE: Single core-hole\index{core hole} calculations are 1838performed as RAS calculations where the opened core orbital is in 1839the RAS1 space. The RAS1 space must therefore contain one and 1840only one orbital when the COREHOLE option is used, and the 1841occupation must be restricted to be exactly one electron. The 1842orbital identified as the core orbital must be either inactive or 1843the one RAS1 orbital, if it is inactive it will switch places with 1844the one RAS1 orbital. The core orbital (now in RAS1) will be 1845frozen in the following optimization. After this calculation has 1846converged, the CORERELAX option may be added and the core orbital 1847will be relaxed\index{relaxed core hole}. When CORERELAX is 1848specified it is assumed that the calculation was preceded by a 1849frozen core\index{frozen core hole} calculation, and that the 1850orbital has already been moved to the RAS1 space. Default 1851corresponds to the main peak, shake-up energies may be obtained by 1852specifying \quotekw{\Key{STATE}} larger than one. Absorption is 1853very beneficial in core hole calculations because of the large 1854orbital relaxation following the opening of the core hole. 1855 1856ABSORPTION: Absorption\index{orbital absorption} level 1 includes occupied - occupied rotations 1857only (including active-active rotations); level 2 adds inactive - 1858secondary rotations and only active - secondary rotations are excluded 1859at this level; and finally level 3 includes all non-redundant rotation 1860for the frozen CI vector. Levels 1 and 2 require the same integral 1861transformation (because the inactive - secondary rotations are 1862performed using the P-supermatrix integrals) and level 1 is therefore 1863usually not used. Level 3 is the normal and full level, but it can be 1864advantageous to activate level 2 together with level 3 if big 1865inactive-active or occupied-occupied rotations are expected. 1866 1867ORB\_TRIAL: Orbital trial\index{orbital trial vector}\ vectors as 1868start vectors can be used for 1869excited states and other calculations with more than one simultaneous 1870roots. The orbital start trial vectors are based on the eigenvectors of 1871the NEO matrix in the previous macro iterations. However, they are 1872probably not cost-effective for multiconfiguration calculations where 1873optimal orbital trial\index{optimal orbital trial vector} vectors are 1874used and they are therefore not used 1875by default. 1876 1877If \quotekw{\Key{SUPSYM}} is specified, then 1878{\sir} automatically identifies "super symmetry"\index{super symmetry!orbitals}, 1879{\it i.e.\/} it assigns orbitals to the irreps of the true point 1880group of the molecule\index{symmetry!group} which is a 1881"super group" of the Abelian group used in the calculation. 1882Degenerate orbitals will be averaged and the "super symmetry" 1883will be enforced in the orbitals. 1884Note that "super symmetry" can only be used 1885in the RHF, MP2, MCSCF, and RESPONS modules, and should 1886not be invoked if other modules are used, 1887for example, if \Sec{*PROPERTIES} (\aba) is invoked. 1888%hj aug 04: it should be OK for closed shell cases, also for CC ??? 1889% it is only for spatially degenerate states that elements 1890% of the orbital gradient may be non-zero, right ??? 1891Also, it cannot be used 1892in finite field calculations where the field lowers the symmetry. 1893The initial orbitals must be symmetry orbitals, and the super symmetry 1894analysis is performed on the kinetic energy matrix in this basis. 1895The \quotekw{.THRSSY} option is used to define when the kinetic 1896energy matrix element between two orbitals is considered to be 1897zero and when two diagonal matrix elements are degenerate. In the 1898first case the orbitals can belong to different irreps of the 1899supergroup and in the second case the two orbitals are considered 1900to be degenerate. The analysis will fail if there are accidental 1901degeneracies in diagonal elements. This can happen if the nuclear 1902geometry deviates slightly from a higher symmetry point group, for 1903example because too few digits has been used in the input of the 1904nuclear geometry. If the program stops because the super symmetry 1905analysis fails with a degeneracy error, you might consider to use 1906more digits in the nuclear coordinates, to change \kw{THRSSY}, or 1907to disable super symmetry by not using \quotekw{.SUPSYM}. The value of 1908\kw{THRSSY} should be sufficiently small to avoid accidental 1909degeneracies and sufficiently large to ignore small errors in 1910geometry and numerical round-off errors. 1911 1912 1913SYM CHECK: The symmetry check is performed on the matrix element 1914$\langle VEC1 \mid oper \mid VEC2\rangle$, where "oper" is 1915the CI-diagonal. 1916It is recommended and the default to use \quotekw{\Key{SYM CHECK}} 1917for excited states, including 1918CI vectors of undesired symmetries is a waste of CPU time. 1919 1920DETERMINANTS: The kernels of the CI sigma routines and density matrix 1921routines are always performed in determinant\index{determinants} 1922basis. However, this 1923keyword specifies that the external representation is Slater 1924determinants as well. The default is that the external representation 1925is in CSF\index{CSF}\index{configuration state function} basis as 1926described in chapter 8 of MOTECC-90. The external 1927CSF\index{CSF}\index{configuration state function} basis is 1928generally to be preferred to be sure that the converged 1929state(s) have pure and correct spin symmetry\index{spin symmetry}, and 1930to save disk space. 1931It is recommended to specify \quotekw{\Key{PLUS COMBINATIONS}} under 1932\quotekw{\Sec{CI VECTOR}} for 1933calculations on singlet states\index{singlet state} with 1934determinants\index{determinants}, 1935in particular for 1936excited singlet\index{excited state} states which often have lower lying triplet states. 1937 1938 1939\pagebreak[3] 1940\subsection{\label{ref-orbinp}\Sec{ORBITAL INPUT}} 1941 1942{\bf Purpose:} 1943 1944To define an initial set of molecular orbitals\index{molecular orbital!initial set} 1945and to control frozen orbitals\index{frozen orbitals}, deletion of orbitals\index{delete orbitals}, 1946reordering and punching of orbitals. 1947 1948\begin{description} 1949\item[\Key{5D7F9G}] 1950 Delete unwanted components in Cartesian d, f, and g orbitals. 1951 (s in d; p in f; s and d in g). By default, \her\ provides atomic 1952 integrals in spherical basis, and this option should therefore not 1953 be needed nowadays. 1954 1955\item[\Key{AO DELETE}] \ \\ 1956 \kw{READ (LUINP,*) THROVL } \\ 1957 Delete MO's based on canonical orthonormalization using eigenvalues 1958 and eigenvectors of the AO overlap matrix.\index{linear dependence} \\ 1959 THROVL: limit for basis 1960 set numerical linear dependence (eigenvectors with eigenvalue less 1961 than THROVL are excluded). Default is 1.0$\cdot$10$^{-6}$. 1962 1963\item[\Key{CMOMAX}] \ \\ 1964 \kw{READ (LUINP,*) CMAXMO} \\ 1965 Abort calculation if the absolute value of any initial MO coefficient is 1966 greater than CMAXMO (default : CMAXMO = $10^3$). Large MO coefficients 1967 can cause significant loss of accuracy in the two-electron integral 1968 transformation. 1969 1970\item[\Key{DELETE}] \ \\ 1971 \kw{READ (LUINP,*) (NDEL(I),I = 1,NSYM) } \\ 1972 Delete orbitals\index{deleted orbitals}, {\it i.e.\/} number of molecular orbitals 1973 in symmetry \quotekw{I} is number of basis functions in symmetry \quotekw{I} minus 1974 \quotekw{NDEL(I)}. \\ 1975 Only for use with \quotekw{.MOSTART} options \quotekw{FORM12} or \quotekw{FORM18}, 1976 it cannot be used with \quotekw{H1DIAG}, \quotekw{EWMO}, or \quotekw{HUCKEL}, 1977 and the other restart options as \quotekw{NEWORB} reads this information from file 1978 and this will overwrite what ever was specified here. 1979 1980\item[\Key{FREEZE}] 1981 Default: no frozen orbitals. 1982\begin{verbatim} 1983 READ (LUINP,*) (NNOR(ISYM), ISYM = 1,NSYM) 1984 DO ISYM = 1,NSYM 1985 IF (NNOR(ISYM) .GT. 0) THEN 1986 READ (LUINP,*) (INOROT(I), I = 1,NNOR(ISYM)) 1987 ... 1988 END IF 1989 END DO 1990\end{verbatim} 1991 where \kw{INOROT} = orbital numbers of the orbitals to be 1992 frozen\index{frozen orbitals!MCSCF and SCF} (not rotated) 1993 in symmetry \quotekw{ISYM} both in SCF and MCSCF 1994 after any reordering (counting from 1 in each symmetry).\\ 1995 Must be specified after all options reducing the number of orbitals. 1996 Frozen occupied orbitals in SCF can only be specified in the \Sec{SCF INPUT} input module 1997 and frozen inactive orbitals in MCSCF can only be specified in the \Sec{OPTIMIZATION} 1998 input module. 1999 2000\item[\Key{GRAM-SCHMIDT ORTHONORMALIZATION}] 2001 Default.\\ 2002 Gram--Schmidt orthonormalization\index{orthonormalization!Gram--Schmidt} of input orbitals. 2003 2004\item[\Key{LOCALIZATION}] \ \\ 2005 \kw{READ (LUINP,*) REWORD} \\ 2006 Specify that the doubly occupied (inactive) orbitals should be localized after SCF 2007 or MCSCF is converged. 2008 Two options for localization of the orbitals are currently available: 2009 \begin{description} 2010 \item[{\tt BOYLOC\ }] Use the Boys localization scheme~\cite{Boyloc}. 2011 %\item[{\tt PIPLOC\ }] Use the Pipek-Mezey localization scheme~\cite{}. 2012 % aug 04: PIPLOC is not implemented yet. 2013 \item[{\tt SELECT\ }] Select a subset of the orbitals to be localized. The first 2014 line following this option contains the number orbitals to localize per symmetry, 2015 and the following lines contain which orbitals to localize within each symmetry, 2016 one line per symmetry with orbitals to localize. 2017 This option is typically used for localizing degenerate 2018 core orbitals, leaving all other orbitals intact. 2019 \begin{verbatim} 2020 READ(LUCMD,*)(NBOYS(I),I=1,NSYM) 2021 DO I=1,NSYM 2022 IF (NBOYS(I).GT.0) THEN 2023 READ(LUCMD,*)(BOYSORB(J,I),J=1,NBOYS(I)) 2024 END IF 2025 END DO 2026 \end{verbatim} 2027 \end{description} 2028 2029\item[\Key{MOSTART}] 2030 Molecular orbital input\index{molecular orbital}\\ 2031 \kw{READ (LUINP,'(1X,A6)') RWORD} \\ 2032 where RWORD is one of the following: 2033 \begin{description} 2034 \item[{\tt FORM12\ }] Formatted input (6F12.8) supplied after 2035 \Sec{*MOLORB} or \Sec{*NATORB} keyword. Use also \quotekw{.DELETE} 2036 if orbitals were deleted. 2037 \item[{\tt FORM18\ }] Formatted input (4F18.14) supplied after 2038 \Sec{*MOLORB} or \Sec{*NATORB} keyword. Use also \quotekw{.DELETE} 2039 if orbitals were deleted. 2040 \item[{\tt EWMO\ }] Start orbitals generated by projecting the EWMO 2041 H{\"u}ckel eigenvectors in a good generally contracted ANO basis set 2042 onto the present basis set. 2043 The EWMO model generally works better than the EHT model. 2044 Default initial guess for molecules in which all atoms have a nuclear charge 2045 less than or equal to 36. 2046 Note: EWMO/HUCKEL is not implemented yet if any element has a 2047 charge larger than 36). 2048 The start density will thus be close to one generated from atomic densities, 2049 but with molecular valence interaction in the EWMO model. 2050 This works a lot better than using a minimal basis set for EWMO. 2051 \item[{\tt HUCKEL\ }] Start orbitals generated by projecting the EHT 2052 H{\"u}ckel eigenvectors in a good generally contracted ANO basis set 2053 onto the present basis set. 2054 Note: EWMO/HUCKEL is not implemented yet if any element has a 2055 charge larger than 36. 2056 The start density will thus be close to one generated from atomic densities, 2057 but with molecular valence interaction in the H{\"u}ckel model. 2058 This works a lot better than using a minimal basis set for H{\"u}ckel. 2059 \item[{\tt H1DIAG\ }] Start orbitals that diagonalize 2060 one-electron Hamiltonian matrix (default 2061 for molecules containing elements with a nuclear larger than 36). 2062 \item[{\tt NEWORB\ }] Input from {\sir} restart file 2063 (\verb|SIRIUS.RST| file) with label \quotekw{NEWORB } 2064 \item[{\tt OLDORB\ }] Input from {\sir} restart file 2065 (\verb|SIRIUS.RST| file) with label \quotekw{OLDORB } 2066 \item[{\tt SIRIFC\ }] Input from {\sir} interface file ("\verb|SIRIFC|") 2067\end{description} 2068 2069\item[\Key{PUNCHINPUTORBITALS}] 2070 Punch input orbitals with label \Sec{*MOLORB}, Format (4F18.14). 2071 These orbitals may {\it e.g.\/} be transferred to another computer and 2072 read there with \quotekw{.MOSTART} followed by \quotekw{ FORM18} on 2073 next line from this input section. 2074 2075\item[\Key{PUNCHOUTPUTORBITALS}] 2076 Punch final orbitals with label \Sec{*MOLORB}, Format (4F18.14). 2077 These orbitals may {\it e.g.\/} be transferred to another computer and 2078 read there with \quotekw{.MOSTART} followed by \quotekw{ FORM18} on 2079 next line from this input section. 2080 2081\item[\Key{REORDER}] 2082Default: no reordering. 2083\begin{verbatim} 2084 READ (LUINP,*) (NREOR(I), I = 1,NSYM) 2085 DO I = 1,NSYM 2086 IF (NREOR(I) .GT. 0) THEN 2087 READ (LUINP,*) (IMONEW(J,I), IMOOLD(J,I), J = 1,NREOR(I)) 2088 END IF 2089 END DO 2090 NREOR(I) = number of orbitals to be reordered in symmetry I 2091 IMONEW(J,I), IMOOLD(J,I) are orbital numbers in symmetry I. 2092 2093For example if orbitals 1 and 5 in symmetry 1 should change place, specify 2094.REORDER 2095 2 0 0 0 2096 1 5 5 1 2097\end{verbatim} 2098 Reordering of molecular orbitals (see comments). 2099 2100\item[\Key{SYMMETRIC ORTHONORMALIZATION}] 2101 Default: Gram-Schmidt orthonormalization\\ 2102 Symmetric orthonormalization of input 2103 orbitals\index{orthonormalization!symmetric}. 2104 2105\end{description} 2106 2107 2108\noindent{\bf Comments:} 2109 2110\Key{REORDER}\index{orbital reordering} can for instance be used for 2111linear molecules to interchange 2112undesired delta orbitals among the active orbitals in symmetry 1 with 2113sigma orbitals. Another example is movement of the core orbital to the 2114RAS1 space for core hole calculation. In general, use of this option 2115necessitates a pre-calculation with STOP AFTER MO-ORTHONORMALIZATION and 2116identification of the various orbitals by inspection of the output. 2117 2118 2119\pagebreak[3] 2120\subsection{\label{ref-popinp}\Sec{POPULATION ANALYSIS}} 2121 2122{\bf Purpose:} 2123 2124To direct population analysis\index{population analysis} of the wave function. 2125Requires a set of natural orbitals\index{natural orbitals!population analysis} and their occupation. 2126 2127\begin{description} 2128\item[\Key{ALL}] 2129 Do all options. 2130 2131%\item[\Key{DIPMOM}] 2132% Calculate dipole moments. Note that this requires that the dipole 2133% length integrals are available on the file \verb|AOONEINT|.\index{dipole moment} 2134%Aug 04: not working as far as I know /hjaaj 2135 2136\item[\Key{GROSSALL}] 2137 Do all gross population analysis. Note that this requires that the dipole 2138 length integrals are available on the file \verb|AOPROPER|\index{population analysis} 2139 2140\item[\Key{GROSSMO}] 2141 Do gross MO population analysis.\index{population analysis} 2142 2143\item[\Key{MULLIKEN}] 2144 Do Mulliken population analysis\index{population analysis}\index{population analysis!Mulliken}\index{Mulliken population analysis} 2145 2146\item[\Key{NETALL}] 2147 Do all net population analysis.\index{population analysis} 2148 2149\item[\Key{NETMO}] 2150 Do net MO population analysis.\index{population analysis} 2151 2152\item[\Key{PRINT}] 2153 Default = 1\\ 2154 \kw{READ (LUINP,*) IPRMUL} \\ 2155 Print level for population analysis. 2156 2157%\item[\Key{QUADRP}] 2158% Calculate quadrupole moments. Note that this requires that the quadrupole 2159% integrals are available on the file \verb|AOONEINT|\index{quadrupole moment} 2160%Aug 04: not working as far as I know /hjaaj 2161 2162\item[\Key{VIRIAL}]\index{virial analysis} \ \\ 2163 Do virial analysis. 2164\end{description} 2165 2166\pagebreak[3] 2167\subsection{\label{ref-priinp}\Sec{PRINT LEVELS}} 2168 2169{\bf Purpose:} 2170 2171To control the printing of output. 2172 2173\begin{description} 2174\item[\Key{CANONI}] \ \\ 2175 Generate canonical/natural orbitals if the wave function has 2176 converged\index{canonical orbital}\index{natural orbitals}. 2177 2178\item[\Key{IPRAVE}] \ \\ 2179 \kw{READ (LUINP,*) IPRAVE} \\ 2180 Sets print level for routines used in "super symmetry" averaging 2181 (default is the general print level from \verb|**DALTON|). 2182 2183\item[\Key{IPRCIX}] \ \\ 2184 \kw{READ (LUINP,*) IPRCIX} \\ 2185 Sets print level for setup of determinant/CSF index information (default = 0). 2186 (default is the general print level from \verb|**DALTON|). 2187 2188\item[\Key{IPRCNO}] \ \\ 2189 \kw{READ (LUINP,*) IPRCNO} \\ 2190 Sets print level for \quotekw{.TRACI} option. 2191 To print the natural orbital occupations in each iteration set 2192 IPRCNO = 1, higher values will give more print. 2193 (default is the general print level from \verb|**DALTON| plus one). 2194 2195\item[\Key{IPRDIA}] \ \\ 2196 \kw{READ (LUINP,*) IPRDIA} \\ 2197 Sets print level for calculation of CI diagonal 2198 (default is the general print level from \verb|**DALTON| minus one). 2199 2200\item[\Key{IPRDNS}] \ \\ 2201 \kw{READ (LUINP,*) IPRDNS} \\ 2202 Sets print level for calculation of CI density matrices 2203 (default is the general print level from \verb|**DALTON|). 2204 2205%\item[\Key{IPRERR}] \ \\ 2206% \kw{READ (LUINP,*) IPRERR} \\ 2207% Sets print level for statistics in error file, LUERR (default = 1) 2208 2209\item[\Key{IPRFCK}] \ \\ 2210 \kw{READ (LUINP,*) IPRFCK} \\ 2211 Sets print level in the Fock matrix construction routines 2212 (default is the general print level from \verb|**DALTON|). 2213 2214\item[\Key{IPRKAP}] \ \\ 2215 \kw{READ (LUINP,*) IPRKAP} \\ 2216 Sets print level in routines for calculation of optimal orbital trial vectors 2217 (default is the general print level from \verb|**DALTON|). 2218 2219\item[\Key{IPRSIG}] \ \\ 2220 \kw{READ (LUINP,*) IPRSIG} \\ 2221 Sets print level for calculation of CI sigma vectors 2222 (default is the general print level from \verb|**DALTON|). 2223 2224\item[\Key{IPRSOL}] \ \\ 2225 \kw{READ (LUINP,*) IPRSOL} \\ 2226 Sets print level in the solvent contribution parts of the calculation 2227 (default is the general print level from \verb|**DALTON| plus four). 2228 2229\item[\Key{NOSUMMARY}] 2230 No final summary of calculation. 2231 2232\item[\Key{POPPRI}] \ \\ 2233 \kw{READ (LUINP,*) LIM\_POPPRI} \\ 2234 Print Mulliken occupation of the first LIM\_POPPRI atoms in 2235 each SCF iteration. Useful for understanding convergence. 2236 (Default = 16, corresponding to two lines of output). 2237 2238\item[\Key{PRINTFLAGS}] 2239 Default: flags set by general levels in \quotekw{\Key{PRINTLEVELS}} 2240\begin{verbatim} 2241 READ (LUINP,*) NUM6, NUM4 2242 IF (NUM6 .GT. 0) READ (LUINP,*) (NP6PTH(I), I=1,NUM6) 2243 IF (NUM4 .GT. 0) READ (LUINP,*) (NP4PTH(I), I=1,NUM4) 2244\end{verbatim} 2245 Individual print flag settings (debug option). 2246 2247\item[\Key{PRINTLEVELS}] 2248 Default: IPRI6 = 0 and IPRI4 = 5 \\ 2249 \kw{READ (LUINP,*) IPRI6,IPRI4 } \\ 2250 Print levels on units LUW6 and LUW4, respectively. 2251% 2252%\item[\Key{PRINTUNITS}] 2253% \kw{READ (LUINP,*) LUW6,LUW4 } \\ 2254% Unit numbers for general output and summary output, respectively 2255% (default: LUW4 = 6 and LUW6 = 6). 2256% 2257\item[\Key{THRPWF}] \ \\ 2258 \kw{READ (LUINP,*) THRPWF} \\ 2259 Threshold for printout of wave function CI coefficients (default = 0.05). 2260 \end{description} 2261 2262 2263 2264%\ifsolvent 2265\pagebreak[3] 2266\subsection{\label{ref-rhfinp}\Sec{SCF INPUT}} 2267 2268{\bf Purpose:} 2269 2270This section deals with the closed shell, one open shell and 2271high--spin spin-restricted 2272Hartree--Fock cases\index{SCF}\index{HF}\index{Hartree--Fock} 2273and Kohn-Sham DFT\index{DFT}. 2274The input here will usually only be used if either 2275\quotekw{\Key{DFT}} or \quotekw{\Key{HF}} 2276has been specified under \quotekw{\Sec{*WAVE FUNCTIONS}} 2277(though it is also needed for MP2 calculations based on saved closed-shell HF 2278orbitals). 2279High--spin spin-restricted open-shell Hartree--Fock or Kohn--Sham DFT calculations are activated by 2280using the \quotekw{.SINGLY OCCUPIED} described here. 2281Other single configuration cases with more than one open shell\index{open shell!SCF} 2282can be handled by the general \quotekw{\Key{MCSCF}} option, by appropriate specifications 2283in the \Sec{CONFIGURATION INPUT} section. 2284 2285\begin{description} 2286\item[\Key{AUTOCCUPATION}] 2287 Default for SCF calculations starting from extended H\"{u}ckel, EWMO, or H1DIAG 2288 starting orbitals. 2289 2290 Allow the distribution of the Hartree--Fock/DFT occupation numbers over 2291 symmetries\index{Hartree--Fock occupation}\index{HF occupation} to 2292 change based on changes in orbital ordering during DIIS\index{DIIS} optimization. 2293 This keyword is incompatible with \quotekw{.SINGLY OCCUPIED} and \quotekw{.COREHOLE}, or 2294 if the HF calculation is followed by CI or MCSCF. 2295 2296%\item[\Key{EDIIS}] 2297% Use a from Kudin {\it et al.} slightly modified (E)DIIS-scheme. 2298% Keys associated with DIIS are also valid for EDIIS (e.g. MXDIIS etc.) 2299 2300\item[\Key{C2DIIS}] 2301 Use Harrell Sellers' C2-DIIS algorithm instead of Pulay's C1-DIIS algorithm 2302 (see comments). 2303 2304\item[\Key{COREHOLE}] \ \\ 2305 \kw{READ (LUINP,*) JCHSYM,JCHORB} \\ 2306 JCHSYM = symmetry of core orbital\\ 2307 JCHORB = the orbital in symmetry JCHSYM with a single core hole\\ 2308 Single core hole\index{core hole} open shell RHF calculation, \quotekw{\Key{OPEN 2309 SHELL}} must not 2310 be specified. The specified core orbital must be 2311 inactive\index{inactive orbital}. 2312 The number of doubly occupied orbitals in symmetry \kw{JCHSYM} will be reduced with one 2313 and instead an open shell orbital will be added for the core hole orbital. 2314 If the specified core orbital is not the last occupied orbital in symmetry 2315 \kw{JCHSYM} it will switch places with that orbital and user-defined reordering 2316 is not possible. 2317 If explicit reordering is required you must also reorder 2318 the core orbital yourself and let \kw{JCHORB} point to the last occupied orbital 2319 of symmetry \kw{JCHSYM}. See comments below. 2320 2321\item[\Key{CORERELAX}] 2322 (ignored if \quotekw{\Key{COREHOLE}} isn't also specified)\\ 2323 Optimize core hole\index{core hole} state with relaxed 2324 core\index{relaxed core} orbital using Newton-Raphson algorithm. 2325 It is assumed that this calculation follows an optimization 2326 with frozen core orbital and the specific value of 2327 \quotekw{JCHORB} under \quotekw{\Key{COREHOLE}} is ignored (no 2328 reordering will take place). 2329 2330%\item[\Key{DIRFOCK}] \ \\ 2331% Direct Fock matrix constructions (recalculate integrals when needed). 2332% Default: AO integrals or P-supermatrix integrals read from disk. 2333%\fi 2334 2335\item[\Key{DOUBLY OCCUPIED}] \ \\ 2336 \kw{READ (LUINP,*) (NRHF(I),I=1,NSYM)} \\ 2337 \index{HF}\index{SCF}\index{Hartree--Fock}\index{MP2}\index{M{\o}ller-Plesset!second-order} 2338 Explicit specification of number of doubly occupied orbitals in each symmetry 2339 for DFT, RHF and MP2 calculations. This keyword 2340 is required when Hartree--Fock or MP2 is part of a multistep 2341 calculation which includes an MCSCF wave function. 2342 Otherwise the program by default will try to guess the occupation, 2343 corresponding to the \quotekw{.AUTOCC} keyword. 2344 2345\item[\Key{ELECTRONS}] \ \\ 2346 \kw{READ (LUINP,*) NRHFEL} \\ 2347 Number of electrons in the molecule\index{electrons in molecule}. 2348 By default, this number will be determined on the basis of the nuclear 2349 charges and the total charge of the molecule\index{charge of molecule} 2350 as specified in the \molinp\ file. 2351 The keyword is incompatible with the keywords \quotekw{.DOUBLY OCCUPIED}, 2352 \quotekw{.OPEN SHELL}, and \quotekw{.SINGLY OCCUPIED}. 2353 2354\item[\Key{FC MVO}] \ \\ 2355 \kw{READ (LUINP,*) (NMVO(I), I = 1,NSYM)} \\ 2356 Modified virtual orbitals using Bauschlichers suggestion 2357 (see Ref.~\cite{cwbjcp72}) 2358 for CI or for start guess for MCSCF. The modified virtual orbitals 2359 are obtained by diagonalizing the virtual-virtual 2360 block of the Fock matrix constructed from NMVO(1:NSYM) doubly 2361 occupied orbitals. 2362 The occupied SCF orbitals (i.e those specified with 2363 \quotekw{.DOUBLY OCCUPIED} and \quotekw{.OPEN SHELL} 2364 or by automatic occupation) are not modified. 2365 The construction of modified virtual orbitals 2366 will follow any SCF and MP2 calculations. 2367 See comments below. 2368 2369\item[\Key{FOCK ITERATIONS}] \ \\ 2370 \kw{READ (LUINP,*) MAXFCK} \\ 2371 Maximum number of closed-shell Roothaan\index{Roothaan iteration} 2372 Fock iterations (default = 0). 2373 2374\item[\Key{FROZEN CORE ORBITALS}] \ \\ 2375 \kw{READ (LUINP,*) (NFRRHF(I),I=1,NSYM)} \\ 2376 Frozen orbitals per symmetry (if MP2 follows then at least these orbitals 2377 must be frozen in the MP2 calculation). 2378 NOTE: no Roothaan Fock iterations allowed if frozen orbitals. 2379 2380\item[\Key{H1VIRT}] Use the virtual orbitals that diagonalize the 2381 one-electron Hamiltonian operator. 2382 2383\item[\Key{MAX DIIS ITERATIONS}] \ \\ 2384 \kw{READ (LUINP,*) MXDIIS} \\ 2385 Maximum number of DIIS iterations\index{iteration number!DIIS, max}\index{DIIS!max iterations} (default = 60). 2386 2387\item[\Key{MAX ERROR VECTORS}] \ \\ 2388 \kw{READ (LUINP,*) MXEVC} \\ 2389 Maximum number of DIIS error vectors\index{DIIS!error vectors, max} 2390 (default = 10, if there is sufficient memory available to hold these 2391 vectors in memory). 2392 2393\item[\Key{MAX MACRO ITERATIONS}] \ \\ 2394 \kw{READ (LUINP,*) MXHFMA} \\ 2395 Maximum number of QCSCF macro\index{iteration number!QCSCF macro, max} 2396 iterations (default = 15). 2397 2398 2399\item[\Key{MAX MICRO ITERATIONS}] \ \\ 2400 \kw{READ (LUINP,*) MXHFMI} \\ 2401 Maximum number of QCSCF\index{SCF!quadratic convergent} micro iterations per macro iteration (default = 12). 2402 2403\item[\Key{NODIIS}] 2404 Do not use DIIS algorithms\index{DIIS} (default: use DIIS algorithm). 2405 2406\item[\Key{NONCANONICAL}] 2407 No transformation to canonical orbitals\index{canonical orbital}. 2408 2409\item[\Key{NOQCSCF}] 2410 No quadratically convergent SCF\index{SCF!no quadratically convergent} iterations. 2411 Default is to switch to QCSCF if DIIS doesn't converge. 2412 2413\item[\Key{OPEN SHELL}] 2414 Default = no open shell\\ 2415 \kw{READ (LUINP,*) IOPRHF} \\ 2416 Symmetry of the open shell in a one open shell\index{open shell!HF}\index{HF!open shell} 2417 calculation. See also \quotekw{.SINGLY OCCUPIED} for high-spin ROHF with more than one 2418 singly occupied orbital. 2419 2420\item[\Key{PRINT}] \ \\ 2421 \kw{READ (LUINP,*) IPRRHF} \\ 2422 Resets general print level to \verb|IPRRHF| in Hartree--Fock/DFT calculations 2423 (default is the general print level from \verb|**DALTON| minus one). 2424 2425\item[\Key{SHIFT}] \ \\ 2426 \kw{READ (LUINP,*) SHFTLVL} \\ 2427 Initial value of level-shift parameter in DIIS iterations. 2428 The default value is 0.0D0 (no level shift). 2429 May be tried if convergence problems in DIIS. The value is added 2430 to the diagonal of the occupied part of the Fock matrix before 2431 Roothaan diagonalization, reducing the mixing of occupied and 2432 virtual orbitals (step restriction). 2433 NOTE that the value should thus be negative. The DIIS routines 2434 will automatically invoke level-shifting (step restriction) if 2435 DIIS seems to be stalling. 2436 2437\item[\Key{SINGLY OCCUPIED}] Default = no singly occupied orbitals \\ 2438 \kw{READ (LUINP,*) (NROHF(I),I=1,NSYM)} \\ 2439 High--spin spin-restricted open-shell Hartree--Fock (aka HSROHF, ROHF) 2440 or Kohn-Sham DFT (aka HSROKS, HSRODFT, RODFT, ROKS). 2441 \index{HSROHF}\index{HSRODFT}\index{HSROKS}\index{ROHF!high spin}\index{RODFT!high spin}\index{ROKS!high spin} 2442 Specify the number of singly occupied orbitals in each irreducible representation 2443 of the molecular point group. Only the high-spin state of these 2444 singly-occupied orbitals will be made and used in the calculations. 2445 We recommend to always run high-spin open-shell geometry optimizations as direct calculations 2446 (\quotekw{\Key{DIRECT}} under \quotekw{\Sec{DALTON}}), 2447 because analytical molecular gradients are only implemented for direct calculations 2448 (numerical gradients will be used for non-direct calculations). 2449 2450\item[\Key{THRESH}] 2451 Default = 1.0D-05 (1.0D-06 if MP2)\\ 2452 \kw{READ (LUINP,*) THRRHF} \\ 2453 Hartree--Fock/DFT convergence threshold for energy gradient. The convergence 2454 of the energy will be approximately the square of this number. 2455 2456\end{description} 2457 2458 2459\noindent{\bf Comments:} 2460 2461By default, the RHF/DFT part of a calculation will consist of : 2462\begin{enumerate} 2463\item {MAXFCK Roothaan Fock iterations (early exit if convergence 2464 or oscillations). However, the default is that no Roothaan Fock 2465iterations are done unless explicitly requested through the keyword 2466\quotekw{.FOCK I}. 2467} 2468\item {MXDIIS DIIS iterations (exit if convergence, {\it i.e.\/} gradient norm 2469 less than THRRHF, and if convergence rate too slow or even diverging). 2470} 2471\item {Unless NOQCSCF, quadratically convergent Hartree--Fock/DFT until 2472 gradient norm less than THRRHF. 2473} 2474\item{If \quotekw{.FC MVO} has been specified 2475 then the virtual SCF orbitals will be modified by diagonalizing 2476 the virtual-virtual block of 2477 a modified Fock matrix: the Fock matrix 2478 based on the occupied orbitals specified after the keyword, a 2479 good choice is the inactive (doubly occupied) orbitals in the 2480 following CI or MCSCF. 2481 The occupied SCF orbitals will not be modified. 2482 If the RHF calculation is followed by a CI or an MCSCF calculation, 2483 \quotekw{.FC MVO} will usually provide much 2484 better start orbitals than the canonical orbitals (canonical 2485 orbitals will usually put diffuse, non-correlating orbitals in the 2486 active space). \\ 2487 WARNING: if both \quotekw{.MP2} and \quotekw{.FC MVO} are specified, 2488 then the MP2 orbitals will be destroyed and replaced with \quotekw{.FC MVO} 2489 orbitals. 2490} 2491\end{enumerate} 2492 2493In general \quotekw{.DOUBLY OCCUPIED} should be specified for CI or MCSCF 2494\index{HF occupation}\index{Hartree--Fock occupation}\index{CI}\index{MCSCF} 2495\index{Configuration Interaction} 2496wave function calculations -- you anyway need to know the distribution 2497of orbitals over symmetries to specify the \quotekw{*CI INPUT} input. 2498For RHF\index{RHF}\index{SCF}\index{Hartree--Fock} 2499or MP2\index{MP2}\index{M{\o}ller-Plesset!second-order} 2500calculations the orbital occupation will be determined on the 2501basis of the nuclear charges and molecular charge of the molecule as 2502specified in the \molinp\ file. 2503 2504By default, starting orbitals and initial orbital occupation will 2505be determined automatically on the basis of a H\"{u}ckel\index{H\"{u}ckel} 2506calculation (for molecules where all nuclear charges are 2507less than or equal to 36), corresponding to the \quotekw{.AUTOCC} keyword. 2508\index{starting orbitals!SCF}\index{H\"{u}ckel!starting orbitals}. 2509If problems is experienced due to the 2510H\"{u}ckel starting guess, it can be avoided by requiring another set of 2511starting orbitals ({\it e.g.\/} \verb|H1DIAG|). 2512 2513%The default convergence threshold is quite sharp (compare with the 2514%default for MCSCF), this is done in order to have good orbitals 2515%for MP2 calculations. For Hartree--Fock 2516%calculations with many basis functions 2517%which are not to be followed by MP2 or used for finite difference 2518%property calculations, some CPU time may be save by lowering the 2519%threshold to the minimum acceptable accuracy. 2520 2521It is our experience that 2522it is usually most efficient not to perform any Roothaan Fock iterations 2523before DIIS is activated, therefore, MAXFCK = 0 as default. 2524The algorithm described in 2525Harrell Sellers, Int. J. Quant. Chem. {\bf 45}, 31-41 (1993) is 2526also implemented, and may be selected with \quotekw{\Key{C2DIIS}}. 2527 2528 2529FC MVO: This option can be used without a Hartree--Fock calculation 2530to obtain compact virtual orbitals, but \quotekw{.DOUBLY OCCUPIED} must be 2531specified anyway in order to identify the virtual orbitals to be transformed. 2532 2533COREHOLE: Enable SCF 2534single core-hole\index{core hole} calculations. To perform 2535an SCF core hole calculation just add the \quotekw{\Key{COREHOLE}} 2536keyword to the input for the closed-shell RHF ground state 2537calculation, specifying from which orbital to remove an electron, 2538and provide the program with the ground state orbitals using the 2539appropriate \quotekw{\Key{MOSTART}} option (normally \kw{NEWORB}). 2540Note that this is different from the MCSCF version of 2541\quotekw{\Key{COREHOLE}} under \quotekw{\Sec{OPTIMIZATION}} 2542(p.~\pageref{ref-optinp}); in the MCSCF case the user must 2543explicitly move the core hole orbital from the inactive class to 2544RAS1 by modifying the \quotekw{\Sec{CONFIGURATION INPUT}} 2545(p.~\pageref{ref-wavinp}) specifications between the initial 2546calculation with filled core orbitals and the core hole 2547calculation. The core hole\index{core hole} orbital will be 2548frozen\index{frozen core hole} in the following optimization. 2549After this calculation has converged, the CORERELAX option may be 2550added and the core orbital will be relaxed\index{relaxed core hole}. 2551When CORERELAX is specified it is assumed that the 2552calculation was preceded by a frozen core calculation, and that 2553the orbital has already been moved to the open shell orbital. Only 2554the main peak can be obtained in SCF calculations, for shake-up 2555energies MCSCF must be used. 2556 2557\pagebreak[3] 2558\subsection{\label{ref-stexinp}\Sec{STEX INPUT}} 2559 2560{\bf Purpose:} 2561 2562Options for a STEX static exchange calculation. 2563(Note: A STEX calculation may require a sequence of four DALTON calculations, see the test energy\_stex for inspiration.) 2564 2565\begin{description} 2566\item[\Key{XAS}] 2567X-ray absorption spectroscopy. 2568 2569\item[\Key{XES}] 2570X-ray emission spectroscopy. 2571 2572\item[\Key{SHAKE}] 2573Electron shake-up/off spectroscopy. 2574 2575\item[\Key{AUGER}] \ \\ 2576 \kw{READ (LUINP,*) NAUGER, (IAUGER(I),JAUGER(I), I=1,NAUGER)} \\ 2577Auger orbital pairs. 2578 2579\item[\Key{AUGERTEST}] 2580Build RPA matrix. 2581 2582\item[\Key{PRINT}] \ \\ 2583 \kw{READ (LUINP,*) IPRSTX} \\ 2584Print level in STEX routines. 2585 2586\item[\Key{OPEN S}] \ 2587\begin{verbatim} 2588 READ (LUINP,*) NOPEN(1:NSYM) 2589 do isym = 1, nsym 2590 if (nopen(isym) > 0) then 2591 READ (LUINP,*) IOPEN(1:NOPEN(ISYM),ISYM) 2592 end if 2593 end do 2594\end{verbatim} 2595 Open shells in STEX calculation. 2596 2597\item[\Key{COEFFI}] \ 2598\begin{verbatim} 2599 do isym = 1, nsym 2600 if (nopen(isym) > 0) then 2601 READ (LUINP,*) CJ(1:NOPEN(ISYM)) 2602 READ (LUINP,*) CK(1:NOPEN(ISYM)) 2603 end if 2604 end do 2605\end{verbatim} 2606 Coefficients for modified J and K Fock matrices. 2607 Note: \kw{.OPEN SH} must be specified before this keyword. 2608 2609\item[\Key{AO}] 2610 Save STEX matrices in AO basis (default: save in MO basis). 2611 2612\end{description} 2613 2614 2615\pagebreak[3] 2616\subsection{\label{ref-solinp}\Sec{SOLVENT}} 2617 2618{\bf Purpose:} 2619 2620Model solvent effects with the self-consistent 2621reaction\index{reaction field} field model. 2622Any specification of dielectric constant(s)\index{dielectric constant} 2623will activate this model. 2624 2625\begin{description} 2626\item[\Key{CAVITY}] 2627 Required, no defaults.\\ 2628 \kw{READ (LUINP,*) RSOLAV}\\ 2629 Enter radius of spherical cavity\index{cavity!radius} in atomic units (\bohr{}). 2630 2631\item[\Key{DIELECTRIC CONSTANT}] \ \\ 2632 \kw{READ (LUINP,*) EPSOL}\\ 2633 Enter relevant dielectric constant\index{dielectric constant} of solvent. 2634 2635\item[\Key{INERSINITIAL}] \ \\ 2636 \kw{READ (LUINP,*) EPSOL, EPPN}\\ 2637 Enter the static and optical dielectric constants\index{dielectric constant} of the solvent 2638 for calculation of the initial state defining inertial polarization\index{inertial polarization}. \\ 2639 Note that the optical dielectric constant specified here 2640 only will be used in case there is a calculation of response 2641 properties, for which this is an alternative input to the use of the 2642 keyword \Key{INERSFINAL}. 2643 2644\item[\Key{INERSFINAL}] \ \\ 2645 \kw{READ (LUINP,*) EPSTAT,EPSOL}\\ 2646 Enter the static and optical dielectric\index{dielectric constant} constants of the solvent 2647 for state specific calculation of the final state with inertial polarization 2648 from a previous calculation with \quotekw{\Key{INERSINITIAL}}\index{final polarization}. 2649 This can for example be used to optimize an excited MCSCF electronic state 2650 with inertial polarization from a previous ground state MCSCF calculation. 2651 The "\verb|SIRIFC|" file from the previous calculation with \quotekw{\Key{INERSINITIAL}} 2652 will contain information about the inertial polarization and must be provided for the 2653 \quotekw{\Key{INERSFINAL}} calculation. \\ 2654 This keyword can also be used to specify the static and optical dielectric constants 2655 for non-equilibrium solvation linear, quadratic, or cubic response functions, 2656 see also Sec.~\ref{sec:solvnoneqrsp}, but this is usually easier done with 2657 \quotekw{.INERSINITIAL} (requires only one \dalton\ calculation instead of two). 2658 2659\item[\Key{MAX L}] 2660 Required, no defaults.\\ 2661 \kw{READ (LUINP,*) LSOLMX}\\ 2662 Enter maximum L quantum number in multipole expansion of charge 2663 distribution in cavity. 2664 2665\item[\Key{PRINT}] \ \\ 2666 \kw{READ (LUINP,*) IPRSOL} \\ 2667 Print level in solvent module routines 2668 (default is the general print level from \verb|**DALTON| plus four). 2669\end{description} 2670 2671\noindent{\bf Comments:} 2672 2673One and only one of \quotekw{\Key{DIELECTRIC CONSTANT}}, 2674\quotekw{\Key{INERSINITIAL}}, and \quotekw{\Key{INERSFINAL}} must be 2675specified. 2676%\fi % end of \ifsolvent 2677 2678 2679 2680\pagebreak[3] 2681\subsection{\label{ref-stpinp}\Sec{STEP CONTROL}} 2682 2683{\bf Purpose:} 2684 2685User control of the NEO restricted step optimization. 2686 2687\begin{description} 2688\item[\Key{DAMPING FACTOR}] 2689 Default = 1.0D0\\ 2690 \kw{READ (LUINP,*) BETA} \\ 2691 Initial value of damping (BETA).\index{damping} 2692 2693\item[\Key{DECREMENT FACTOR}] 2694 Default = 0.67D0\\ 2695 \kw{READ (LUINP,*) STPRED} \\ 2696 Decrement factor on trust radius\index{trust radius} 2697 2698\item[\Key{GOOD RATIO}] 2699 Default = 0.8D0 \\ 2700 \kw{READ (LUINP,*) RATGOD} \\ 2701 Threshold ratio for good second order agreement: the trust radius can 2702 be increased if ratio is better than RATGOD. 2703 2704\item[\Key{INCREMENT FACTOR}] 2705 Default = 1.2D0\\ 2706 \kw{READ (LUINP,*) STPINC} \\ 2707 Increment factor on trust radius.\index{trust radius} 2708 2709\item[\Key{MAX DAMPING}] 2710 Default = 1.0D6\\ 2711 \kw{READ (LUINP,*) BETMAX} \\ 2712 Maximum damping value.\index{damping} 2713 2714\item[\Key{MAX STEP LENGTH}] 2715 Default = 0.7D0\\ 2716 \kw{READ (LUINP,*) STPMAX} \\ 2717 Maximum acceptable step length, trust radius will never be larger than 2718 STPMAX even if the ratio is good as defined by GOOD RATIO. 2719 2720\item[\Key{MIN DAMPING}] 2721 Default = 0.2D0\\ 2722 \kw{READ (LUINP,*) BETMIN} \\ 2723 Minimum damping value 2724 2725\item[\Key{MIN RATIO}] 2726 Default = 0.4D0 for ground state, 0.6 for excited states\\ 2727 \kw{READ (LUINP,*) RATMIN} \\ 2728 Threshold ratio for bad second order agreement: the trust radius is 2729 to be decreased if ratio is worse than RATMIN. 2730 2731\item[\Key{NO EXTRA TERMINATION TESTS}] 2732 Skip extra termination tests and converge micro iterations to 2733 threshold. Normally the micro iterations are terminated if the 2734 reduced NEO matrix has more negative eigenvalues than corresponding 2735 to the desired state, because then we are in a "superglobal" region 2736 and we just want to step as quickly as possible to the region where 2737 the Hessian (and NEO matrix) has the correct structure. Further 2738 convergence is usually wasted. 2739 2740\item[\Key{REJECT THRESHOLD}] 2741 Default = 0.25 for ground state, 0.4 for excited states\\ 2742 \kw{READ (LUINP,*) RATREJ} \\ 2743 Threshold ratio for unacceptable second order agreement: the step 2744 must be rejected if ratio is worse than RATREJ. 2745 2746\item[\Key{THQKVA}] 2747 Default: 8.0 for MCSCF; 0.8 for QCSCF\\ 2748 \kw{READ (LUINP,*) THQKVA} \\ 2749 Convergence factor for micro iterations in local (quadratic) region: 2750 THQKVA*(norm of gradient)**2 2751 2752\item[\Key{THQLIN}] 2753 Default: 0.2\\ 2754 \kw{READ (LUINP,*) THQLIN} \\ 2755 Convergence factor for micro iterations in global (linear) region: \\ 2756 THQLIN*(norm of gradient) 2757 2758\item[\Key{THQMIN}] 2759 Default: 0.1\\ 2760 \kw{READ (LUINP,*) THQMIN} \\ 2761 Convergence threshold for auxiliary roots in NEO MCSCF optimization. 2762 2763\item[\Key{TIGHT STEP CONTROL}] 2764 Tight step control also for ground state calculations 2765 (tight step control is always enforced for excited states) 2766 2767\item[\Key{TOLERANCE}] 2768 Default: 1.1\\ 2769 \kw{READ (LUINP,*) RTTOL} \\ 2770 Acceptable tolerance in deviation of actual step from trust radius 2771 (the default value of 1.1 corresponds to a maximum of 10\% deviation). 2772 2773\item[\Key{TRUST RADIUS}] 2774 Default = STPMAX = 0.7 or, if restart, trust radius determined by previous 2775 iteration.\index{trust radius}\\ 2776 \kw{READ (LUINP,*) RTRUST} \\ 2777 Initial trust radius. 2778 2779\end{description} 2780 2781 2782\pagebreak[3] 2783\subsection{\label{ref-trainp}\Sec{TRANSFORMATION}} 2784 2785{\bf Purpose:} 2786 2787Transformation\index{integral transformation} of two-electron 2788integrals\index{two-electron integral} to molecular orbital 2789basis\index{molecular orbital}. 2790 2791\begin{description} 2792\item[\Key{FINAL LEVEL}] \ \\ 2793 \kw{READ (LUINP,*) ITRFIN} \\ 2794 Final integral transformation\index{integral transformation} level (only active if the keyword 2795 \quotekw{\Key{INTERFACE}} has been specified, or this is an \aba\ or 2796 \resp\ calculation. 2797 2798\item[\Key{LEVEL}] \ \\ 2799 \kw{READ (LUINP,*) ITRLVL} \\ 2800 Integral transformation level (see comments). 2801 2802\item[\Key{OLD TRANSFORMATION}] 2803 Use existing transformed integrals 2804 2805\item[\Key{PRINT}] \ \\ 2806 \kw{READ (LUINP,*) IPRTRA} \\ 2807 Print level in integral transformation module 2808 2809\item[\Key{RESIDENT MEMORY}] \ \\ 2810 \kw{READ (LUINP,*) MWORK} \\ 2811 On virtual memory computers, the transformation will run more 2812 efficiently if it can be kept within the possible resident memory 2813 size: the real memory size. {\sir} will attempt to only use MWORK 2814 double precision words in the transformation. 2815\end{description} 2816 2817 2818\noindent{\bf Comments:} 2819 2820There are several types of integral transformations which may be 2821specified by the two transformation level keywords. 2822\begin{itemize} 2823 \item[0:] CI calculations, MCSCF gradient (default if CI, but 2824 no MCSCF specified). 2825 One index all orbitals, three indices only active 2826 orbitals. 2827 2828 \item[1:] Obsolete, do not use. 2829 2830 \item[2:] Default for MCSCF optimization. All integrals needed for {\sir} 2831 second-order MCSCF optimization, including the integrals 2832 needed to explicitly construct the diagonal of the orbital 2833 Hessian. Two indices occupied orbitals, two indices all 2834 orbitals, with some reduction for inactive indices. 2835 Both (cd/ab) and (ab/cd) are stored. 2836 2837 \item[3:] Same integrals as 2, including also the (ii/aa) and 2838 (ia/ia) integrals for exact inactive-secondary diagonal elements 2839 of the orbitals Hessian. 2840 2841 \item[4:] All integrals with minimum two occupied indices. 2842 2843 \item[5:] 3 general indices, one occupied index. Required for MP2 2844 natural orbital analysis (the MP2 module automatically 2845 performs an integral transformation of this level). 2846 2847 \item[10:] Full transformation. 2848\end{itemize} 2849 2850 2851\pagebreak[3] 2852\subsection{\label{ref-cube}\Sec{CUBE}} 2853 2854{\bf Purpose:} 2855 2856Generates cube file\index{cube file} of total SCF electron density and/or 2857molecular orbitals after SCF calculations. The keyword \quotekw{\Key{INTERFACE}} 2858must be specified. 2859 2860\begin{description} 2861\item[\Key{DENSITY}] 2862 Generates cube file ``\kw{density.cube}'' with total SCF electron density. 2863 2864\item[\Key{HOMO}] 2865 Generates cube file ``\kw{homo.cube}'' with the information of the highest 2866occupied molecular orbitals. 2867 2868\item[\Key{LUMO}] 2869 Generates cube file ``\kw{lumo.cube}'' with the information of the lowest 2870unoccupied molecular orbitals. 2871 2872\item[\Key{MO}] \ \\ 2873 \kw{READ (LUINP,*) IDX\_MO} \\ 2874 Generates cube file ``\kw{mo.cube}'' with specified indices of molecular orbitals 2875by ``\kw{IDX\_MO}''. For instance, valid format is like ``1-6,7,10-12'' only including 2876digits, minus sign and comma. 2877 2878\item[\Key{FORMAT}] \ \\ 2879 \kw{READ (LUINP,*) CUBE\_FORMAT} \\ 2880 Specifies cube file format, only ``\kw{GAUSSIAN}'' (Gaussian cube file format, 2881see\linebreak \verb|http://www.gaussian.com/g_tech/g_ur/u_cubegen.htm|) for the 2882time being. 2883 2884\item[\Key{ORIGIN}] \ \\ 2885 \kw{READ (LUINP,*) CUBE\_ORIGIN} \\ 2886 Reads the coordinates (a.u.) of origin/initial point. 2887 2888\item[\Key{INCREMENT}] \ \\ 2889 \kw{READ (LUINP,*) N1, X1, Y1, Z1} \\ 2890 \kw{READ (LUINP,*) N2, X2, Y2, Z2} \\ 2891 \kw{READ (LUINP,*) N3, X3, Y3, Z3} \\ 2892 Reads the number of increments and increments (a.u.) along three running directions, 2893in which ``\kw{(X1,Y1,Z1)}'' is the slowest running direction, and ``\kw{(X3,Y3,Z3)}'' 2894is the fastest running direction. 2895 2896As described at \verb|http://www.gaussian.com/g_tech/g_ur/u_cubegen.htm|, if the 2897origin/initial point is (X0,Y0,Z0), then the point at (I1,I2,I3) has coordinates: 2898 2899X-coordinate: X0+(I1-1)*X1+(I2-1)*X2+(I3-1)*X3\\ 2900Y-coordinate: Y0+(I1-1)*Y1+(I2-1)*Y2+(I3-1)*Y3\\ 2901Z-coordinate: Z0+(I1-1)*Z1+(I2-1)*Z2+(I3-1)*Z3 2902\end{description} 2903 2904 2905\pagebreak[3] 2906\section{\label{sec:ref-molorbinp} \Sec{*MOLORB} input module} 2907 2908If formatted input of the molecular orbitals has been specified in 2909the \Sec{ORBITAL INPUT} section, then {\sir} will attempt to find 2910the two-star label "\verb|**MOLORB|" in the input file and read 2911the orbital coefficients from the lines following this label. 2912