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52 THE COSMO MODEL 371 The COSMO output file will be written after every converged SCF calculation. The segment charges and potentials are corrected by the outlying charge correction. For the total charges and energies corrected and uncorrected values are given. The normal output file contains uncorrected values only. It is recommended to use the corrected values from the output file. Optimizations: It is recommended to use optimizer that operates with gradients exclusively. Line search techniques that use energies tends to fail, because of the energy discontinuities which may occur due to a reorganization of the segments after a geometry step. For the same reasons numerical gradients are not recommended. 52.1 BASIC THEORY COSMO is a continuum solvation model, in which the solvent is represented as a dielectric continuum of permittivity ε. The solute molecule is placed in a cavity inside the continuum. The response of the continuum due to the charge distribution of the solute is described by the generation of a screening charge distribution on the cavity surface. This charge distribution can be calculated by solving the boundary equation of vanishing electrostatic potential on the surface of a conductor. After a discretization of the cavity surface into sufficiently small segments, the vector of the screening charges on the surface segments is q ∗ = −A −1 Φ where Φ is the vector of the potential due to the solute charge distribution on the segments, and A is the interaction matrix of the screening charges on the segments. This solution is exact for an electric conductor. For finite dielectrics the true dielectric screening charges can be approximated very well by scaling the charge density of a conductor with f (ε). q = f (ε)q ∗ ; f (ε) = (ε − 1)/(ε + 0.5) In every SCF step the screening charges q have to be generated from the potential Φ, and then added to the Hamiltonian as external point charges. The total energy of the system is E tot = E 0 + E diel ; E diel = 1 2 Φq where E 0 is the bare self-energy of the system and E diel the dielectric energy. Cavity construction: First a surface of mutually excluding spheres of radius R i + rsolv is constructed, where the R i are the radii of the atoms, defined as element specific radii and rsolv is some radius representing a typical maximum curvature of a solvent molecular surface. rsolv should not be misinterpreted as a mean solvent radius, nor modified for different solvents. Every atomic sphere is represented by an underlying basis grid of nppa points per full atom. Basis grid points which intersect a sphere of a different atom are neglected. In a second step the remainder of the basis grid points are projected to the surface defined by the radii R i . As a third step of the cavity construction the remaining basis grid points are gathered to segments, which are the areas of constant screening charges in the numerical solution. Finally, the intersection seams between the atoms are filled with additional segments. Now the A-matrix can be set up. The matrix elements will be calculated from the basis grid points of the segments for close and medium segment distances (governed by the disex value),
52 THE COSMO MODEL 372 or using the segment centres for large segment distances. Outlying charge correction: The non vanishing electron density outside the cavity causes an error that can be corrected by the outlying charge correction. This correction uses the potential on the so called outer surface (defined by the radii R i + rsolv × routf) to estimate a correction term for the screening charges and the energies (A. Klamt and V. Jonas, J. Chem. Phys., 105, 9972-9981(1996)). The correction will be performed once at the end of a converged SCF calculation. All corrected values can be found in the COSMO output file.
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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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14 INTEGRATION 86 smaller than this
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14 INTEGRATION 88 THR D3EXT THREST
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14 INTEGRATION 90 THRQ2 LMP2 THRAO
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14 INTEGRATION 92 Table 7: Default
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15 DENSITY FITTING 94 DF-HF,DF_BASI
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15 DENSITY FITTING 96 LOCFIT F12 LO
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16 THE SCF PROGRAM 98 16 THE SCF PR
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16 THE SCF PROGRAM 100 16.1.4 Optio
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16 THE SCF PROGRAM 102 16.3 Saving
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16 THE SCF PROGRAM 104 r1=1.85,r2=1
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16 THE SCF PROGRAM 106 16.9.1 Level
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17 THE DENSITY FUNCTIONAL PROGRAM 1
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18 ORBITAL LOCALIZATION 124 geometr
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18 ORBITAL LOCALIZATION 126 GROUP,3
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18 ORBITAL LOCALIZATION 128 18.9 Op
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19 THE MCSCF PROGRAM MULTI 130 f) c
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19 THE MCSCF PROGRAM MULTI 132 19.3
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19 THE MCSCF PROGRAM MULTI 134 WF,6
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19 THE MCSCF PROGRAM MULTI 138 or C
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19 THE MCSCF PROGRAM MULTI 144 icst
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20 THE CI PROGRAM 148 ***,N2 geomet
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20 THE CI PROGRAM 150 and double ex
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20 THE CI PROGRAM 152 refstat: mxsh
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20 THE CI PROGRAM 154 Default is to
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20 THE CI PROGRAM 156 20.3.8 Restri
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20 THE CI PROGRAM 158 DM and NATORB
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20 THE CI PROGRAM 160 ZERO: THRDLP:
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20 THE CI PROGRAM 162 PAIRS=1: prin
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20 THE CI PROGRAM 164 problem is to
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21 MULTIREFERENCE RAYLEIGH SCHRÖDI
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22 NEVPT2 CALCULATIONS 176 IHINT=0
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23 MØLLER PLESSET PERTURBATION THE
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23 MØLLER PLESSET PERTURBATION THE
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24 THE CLOSED SHELL CCSD PROGRAM 18
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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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Page 353 and 354: 42 GEOMETRY OPTIMIZATION (OPTG) 320
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Page 385 and 386: 47 POTENTIAL ENERGY SURFACES (SURF)
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Page 397 and 398: 49 THE VSCF PROGRAM (VSCF) 364 THER
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Page 401 and 402: 50 THE VCI PROGRAM (VCI) 368 surf,s
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Page 407 and 408: 54 THE TDHF AND TDKS PROGRAMS 374 o
Page 409 and 410: 55 ORBITAL MERGING 376 MOVE command
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Page 413 and 414: 56 MATRIX OPERATIONS 380 ***,NO mer
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Page 419 and 420: 56 MATRIX OPERATIONS 386 56.14 Form
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Page 423 and 424: A INSTALLATION GUIDE 390 the result
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Page 439 and 440: B RECENT CHANGES 406 B.1.4 New basi
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Page 447 and 448: C DENSITY FUNCTIONAL DESCRIPTIONS 4
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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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