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19 THE MCSCF PROGRAM MULTI 137 SPIN=ms2 SAVE=record ORBITAL=record PRINT=nvirt Compute natural orbitals for states with the specified spin. ms2 equals 2 ∗ S, i.e., 0 for singlet, 1 for doublet etc. This can be used to together with STATE to select a specific state in case that states of different spin are averaged. If STATE is not specified, the state-averaged density for all states of the given spin is used. Request to save the civector(s) to the specified record. Request to save the orbitals to the specified record (same effect as specifying record as first agrument (see above). Request to print nvirt virtual orbitals in each symmetry. By default, the orbitals are not printed unless the ORBPRINT option (see section 19.8.1 is present or the global GPRINT,ORBITALS (see section 6.12) directive has been given before. The PRINT option on this card applies only to the current orbitals. Several NATORB, CANORB, and LOCORB cards (for different states) may follow each other. In contrast to earlier versions of MOLPRO the different orbital sets can all be stored in one dump record (but different records still work). See section 4.11 for information about dump records and how specific orbital sets can be requested in a later calculation. 19.5.6 Pseudo-canonical orbitals CANORB,[record,] [options] or CANONICAL,[record,] [options] Request to canonicalize the final orbitals, and writing them to record record. All options have the same effect as described for NATORB. 19.5.7 Localized orbitals LOCORB,[record,] [options] or LOCAL,[record,] [options] Request to localize the final orbitals, and writing them to record record. All options have the same effect as described for NATORB. Note: LOCAL is interpreted by MULTI, but LOCALI is a separate command which calls the localization program and not recognized by MULTI. In order to avoid confusion, it is recommended to use LOCORB rather then LOCAL as subcommand within MULTI. 19.5.8 Diabatic orbitals In order to construct diabatic states, it is necessary to determine the mixing of the diabatic states in the adiabatic wavefunctions. In principle, this mixing can be obtained by integration of the non-adiabatic coupling matrix elements. Often, it is much easier to use an approximate method, in which the mixing is determined by inspection of the CI coefficients of the MCSCF
19 THE MCSCF PROGRAM MULTI 138 or CI wavefunctions. This method is applicable only if the orbital mixing is negligible. For CASSCF wavefunctions this can be achieved by maximizing the overlap of the active orbitals with those of a reference geometry, at which the wavefunctions are assumed to be diabatic (e.g. for symmetry reasons). The orbital overlap is maximized using using the new DIAB command in the MCSCF program. Only the active orbitals are transformed. This procedure works as follows: first, the orbitals are determined at the reference geometry. Then, the calculations are performed at displaced geometries, and the ”diabatic” active orbitals, which have maximum overlap with the active orbitals at the reference geometry, are obtained by adding a DIAB directive to the input: Old form (Molpro96, obsolete): DIAB,orbref, orbsav, orb1,orb2,pri New form: DIAB,orbref [,TYPE=orbtype] [,STATE=state] [,SPIN=spin] [,MS2=ms2] [,SAVE=orbsav] [,ORB1=orb1, ORB2=orb2] [,PRINT=pri] [,METHOD=method] Here orbref is the record holding the orbitals of the reference geometry, and orbsav is the record on which the new orbitals are stored. If orbsav is not given (recommended!) the new orbitals are stored in the default dump record (2140.2) or the one given on the ORBITAL directive (see section 19.5.3). In contrast to earlier versions of MOLPRO it is possible that orbref and orbsav are the same. The specifications TYPE, STATE, SPIN can be used to select specific sets of reference orbitals, as described in section 4.11. orb1, orb2 is a pair of orbitals for which the overlap is to be maximized. These orbitals are specified in the form number.sym, e.g. 3.1 means the third orbital in symmetry 1. If orb1, orb2 are not given, the overlap of all active orbitals is maximized. pri is a print parameter. If this is set to 1, the transformation angles for each orbital are printed for each Jacobi iteration. method determines the diabatization method. method=1 (default): use Jacobi rotations; method=2: use block diagonalization. Both methods yield very similar results. method=2 must only be used for CASSCF wavefunctions. method=-1 and method=-2: as the positive values, but AO overlap matrix of the current geometry is used. This minimizes the change of the MO coefficients, rather than maximizing the overlap to the neighbouring orbitals. Using the defaults described above, the following input is sufficient in most cases: DIAB,orbref Using Molpro98 is is not necessary any more to give any GEOM and DISPL cards. The displacements and overlap matrices are computed automatically (the geometries are stored in the dump records, along with the orbitals). The diabatic orbitals have the property that the sum of orbital and overlap contributions in the non-adiabatic coupling matrix elements become approximately zero, such that the adiabatic mixing occurs only through changes of the CI coefficients. This allows to determine the mixing angle directly from the CI coefficients, either in a simple way as described for instance in J. Chem. Phys. 89, 3139 (1988), or in a more advanced manner as described by Pacher, Cederbaum, and Köppel in J. Chem. Phys. 89, 7367 (1988). Recently, an automatic procedure, as described in J. Chem. Phys. 102, 0000, (1999) has been implemented into MOLPRO. This is available in Version 99.1 and later and is described in section 38. Below we present an example for the first two excited states of H 2 S, which have B 1 and A 2 symmetry in C 2v , and A ′′ symmetry in C S . We first perform a reference calculation in C 2v symmetry, and then determine the diabatic orbitals for displaced geometries in C S symmetry. Each subsequent calculation uses the previous orbitals as reference. One could also use the orbitals
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MOLPRO Users Manual Version 2010.1
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ii • Møller-Plesset perturbation
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iv 3. Explicitly correlated LMP2-F1
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vi The original reference to uncont
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viii Rangehybrid methods: T. Leinin
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CONTENTS x 4.12 Summary of keywords
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CONTENTS xii 10.4 Geometry Files .
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CONTENTS xiv 16.9.4 Sanity check on
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CONTENTS xvi 19.5.1 Defining the st
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CONTENTS xviii 20.4 Miscellaneous t
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CONTENTS xx 29.6.3 Manually Definin
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CONTENTS xxii 34.1.5 Printing optio
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CONTENTS xxiv 39.10Point group symm
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CONTENTS xxvi 42.2.7 Numerical Hess
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CONTENTS xxviii 53 QM/MM INTERFACES
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CONTENTS xxx A.3.11 Fedora 13 (32-b
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CONTENTS xxxii C.41 THGFL: . . . .
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2 RUNNING MOLPRO 2 of directories o
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2 RUNNING MOLPRO 4 also some parts
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2 RUNNING MOLPRO 6 Note that option
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3 DEFINITION OF MOLPRO INPUT LANGUA
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4 GENERAL PROGRAM STRUCTURE 14 Glob
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4 GENERAL PROGRAM STRUCTURE 16 in d
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4 GENERAL PROGRAM STRUCTURE 18 Tabl
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4 GENERAL PROGRAM STRUCTURE 20 tion
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4 GENERAL PROGRAM STRUCTURE 22 Prog
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4 GENERAL PROGRAM STRUCTURE 24 LCIS
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5 INTRODUCTORY EXAMPLES 26 In the a
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5 INTRODUCTORY EXAMPLES 28 5.7 Proc
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6 PROGRAM CONTROL 30 ***,h2o benchm
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6 PROGRAM CONTROL 32 6.5 Allocating
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6 PROGRAM CONTROL 34 6.7.1 IF state
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6 PROGRAM CONTROL 36 Certain import
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6 PROGRAM CONTROL 38 ZERO ONEINT TW
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6 PROGRAM CONTROL 40 6.13.1 Example
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6 PROGRAM CONTROL 42 Table 5: One-e
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7 FILE HANDLING 44 7.4 DATA The DAT
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8 VARIABLES 46 Numbers: Logicals: S
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8 VARIABLES 48 8.4 System variables
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8 VARIABLES 50 are valid variable d
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8 VARIABLES 52 CM=1.d0/219474.63067
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8 VARIABLES 54 DEL4 ∇ 4 DARWIN Da
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8 VARIABLES 56 CHARGE NELEC SPIN CI
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9 TABLES AND PLOTTING 58 8.11 Readi
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9 TABLES AND PLOTTING 60 plotted; i
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10 MOLECULAR GEOMETRY 62 PLANEXZ z-
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10 MOLECULAR GEOMETRY 64 geometry s
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10 MOLECULAR GEOMETRY 66 ***,H2O ge
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10 MOLECULAR GEOMETRY 68 entries. D
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11 BASIS INPUT 70 resolution in exp
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11 BASIS INPUT 72 • The Binning/C
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11 BASIS INPUT 74 The specification
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11 BASIS INPUT 76 the exponents of
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11 BASIS INPUT 78 ***,h2o geom={o;
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12 EFFECTIVE CORE POTENTIALS 80 is
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13 CORE POLARIZATION POTENTIALS 82
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14 INTEGRATION 84 14.1 Sorted integ
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Page 125 and 126: 14 INTEGRATION 92 Table 7: Default
Page 127 and 128: 15 DENSITY FITTING 94 DF-HF,DF_BASI
Page 129 and 130: 15 DENSITY FITTING 96 LOCFIT F12 LO
Page 131 and 132: 16 THE SCF PROGRAM 98 16 THE SCF PR
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Page 141 and 142: 17 THE DENSITY FUNCTIONAL PROGRAM 1
Page 157 and 158: 18 ORBITAL LOCALIZATION 124 geometr
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Page 163 and 164: 19 THE MCSCF PROGRAM MULTI 130 f) c
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Page 181 and 182: 20 THE CI PROGRAM 148 ***,N2 geomet
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Page 199 and 200: 21 MULTIREFERENCE RAYLEIGH SCHRÖDI
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25 EXCITED STATES WITH EQUATION-OF-
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27 THE MRCC PROGRAM OF M. KALLAY (M
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28 SMILES 202 This code is not incl
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29 LOCAL CORRELATION TREATMENTS 204
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30 LOCAL METHODS FOR EXCITED STATES
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30 LOCAL METHODS FOR EXCITED STATES
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31 EXPLICITLY CORRELATED METHODS 22
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32 THE FULL CI PROGRAM 244 32 THE F
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33 SYMMETRY-ADAPTED INTERMOLECULAR
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34 PROPERTIES AND EXPECTATION VALUE
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35 RELATIVISTIC CORRECTIONS 268 •
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36 DIABATIC ORBITALS 270 This proce
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37 NON ADIABATIC COUPLING MATRIX EL
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38 QUASI-DIABATIZATION 274 This cal
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38 QUASI-DIABATIZATION 276 ***,h2s
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38 QUASI-DIABATIZATION 278 ***,h2s
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39 THE VB PROGRAM CASVB 280 39 THE
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39 THE VB PROGRAM CASVB 282 configu
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39 THE VB PROGRAM CASVB 284 be proj
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39 THE VB PROGRAM CASVB 286 The lis
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39 THE VB PROGRAM CASVB 288 This ke
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39 THE VB PROGRAM CASVB 290 to writ
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40 SPIN-ORBIT-COUPLING 292 integral
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40 SPIN-ORBIT-COUPLING 294 40.6.1 P
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40 SPIN-ORBIT-COUPLING 296
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41 ENERGY GRADIENTS 298 41 ENERGY G
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41 ENERGY GRADIENTS 300 state2) and
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41 ENERGY GRADIENTS 302 ZMAT OPT3N
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42 GEOMETRY OPTIMIZATION (OPTG) 304
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43 VIBRATIONAL FREQUENCIES (FREQUEN
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45 MINIMIZATION OF FUNCTIONS 340 45
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45 MINIMIZATION OF FUNCTIONS 342 **
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46 BASIS SET EXTRAPOLATION 344 extr
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46 BASIS SET EXTRAPOLATION 346 ***,
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46 BASIS SET EXTRAPOLATION 348 46.3
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46 BASIS SET EXTRAPOLATION 350 geom
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47 POTENTIAL ENERGY SURFACES (SURF)
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48 POLYNOMIAL REPRESENTATIONS (POLY
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49 THE VSCF PROGRAM (VSCF) 364 THER
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50 THE VCI PROGRAM (VCI) 366 CITHR=
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50 THE VCI PROGRAM (VCI) 368 surf,s
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52 THE COSMO MODEL 370 52 THE COSMO
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52 THE COSMO MODEL 372 or using the
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54 THE TDHF AND TDKS PROGRAMS 374 o
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55 ORBITAL MERGING 376 MOVE command
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55 ORBITAL MERGING 378 55.13 Exampl
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56 MATRIX OPERATIONS 380 ***,NO mer
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56 MATRIX OPERATIONS 382 56.2 Loadi
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56 MATRIX OPERATIONS 384 If NATURAL
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56 MATRIX OPERATIONS 386 56.14 Form
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56 MATRIX OPERATIONS 388 ***,h2o ma
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A INSTALLATION GUIDE 390 the result
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A INSTALLATION GUIDE 392 For IA32 L
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A INSTALLATION GUIDE 394 3. If any
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A INSTALLATION GUIDE 396 -gfortran
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A INSTALLATION GUIDE 398 A.3.7 Test
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A INSTALLATION GUIDE 400 --noverbos
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A INSTALLATION GUIDE 402 A.3.12 ope
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A INSTALLATION GUIDE 404 A.3.14 Ins
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B RECENT CHANGES 406 B.1.4 New basi
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B RECENT CHANGES 408 1) · exp(−9
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B RECENT CHANGES 410 B.4 New featur
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B RECENT CHANGES 412 5. Multipole m
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C DENSITY FUNCTIONAL DESCRIPTIONS 4
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+ 9 8 (1 − ζ ) 4/3 C DENSITY FUN
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D LICENSE INFORMATION 456 D.1 BLAS
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D LICENSE INFORMATION 458 D.3 Boost
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INDEX 460 DFTTHRESH, 109 Difference
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INDEX 462 NOGPRINT, 38 NOGRIDSAVE,
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