General: **PROPERTIES

This module controls the main features of the HF, SOPPA, and MCSCF property calculations, that is, which properties is to be calculated. In addition it includes directives affecting the performance of several of the program sections. This includes HF and MCSCF molecular gradients and Hessians. It should be noted, however, that the specification of what kind of walk (minimization, location of transition states, dynamical walks) is given in the *WALK or *OPTIMIZE submodules in the general input module. See also Chapter 7.

See Chapter 27 for specification of CC property calculations.

Note that RESPONSECHAPTER ) IS THE MOST GENERAL PART OF THE CODE FOR CALCULATING MANY DIFFERENT ELECTRONIC LINEAR, QUADRATIC, OR CUBIC MOLECULAR RESPONSE PROPERTIES BASED ON SCF, MCSCF, OR CI WAVE FUNCTIONS OR KOHN-SHAM DFT. SOME OF THESE SCF/MCSCF PROPERTIES CAN ALSO BE REQUESTED FROM THE **PROPERTIES INPUT MODULES DESCRIBED HERE. NOTE: FOR SUCH PROPERTIES YOU SHOULD REQUEST THEM EITHER HERE OR IN **RESPONSE, OTHERWISE YOU WILL CALCULATE THEM TWICE! USUALLY THE OUTPUT IS NICEST HERE IN THE **PROPERTIES MODULE (E.G. COLLECTED IN TABLES AND IN OFTEN USED UNITS, MOST PROPERTIES ARE ONLY GIVEN IN ATOMIC UNITS IN RESPONSE), AND NUCLEAR CONTRIBUTIONS ARE INCLUDED IF RELEVANT. NO NUCLEAR CONTRIBUTIONS ARE ADDED IN RESPONSE. SOME SPECIFIC PROPERTIES, ESPECIALLY THOSE INVOLVING NUCLEAR DERIVATIVES, CAN ONLY BE CALCULATED VIA **PROPERTIES. OTHER PROPERTIES, FOR EXAMPLE QUADRATIC AND CUBIC MOLECULAR RESPONSE FUNCTIONS CAN ONLY BE CALCULATED IN THE **RESPONSE MODULE.

.ALPHA

INVOKES THE CALCULATION OF FREQUENCY DEPENDENT POLARIZABILITIES. COMBINED WITH THE KEYWORD .SOPPA OR .SOPPA(CCSD) IT INVOKES A SOPPA OR SOPPA(CCSD) CALCULATION OF THE FREQUENCY DEPENDENT POLARIZABILITY.

.CAVORG

READ (LUCMD,*) (CAVORG(ICOOR), ICOOR = 1, 3)

READS THE ORIGIN TO BE USED FOR THE CAVITY DURING A SOLVENT CALCULATION. BY DEFAULT THIS IS CHOSEN TO BE THE CENTER OF MASS. SHOULD BY USED WITH CARE, AS IT HAS TO CORRESPOND TO THE CENTER USED IN THE EVALUATION OF THE UNDIFFERENTIATED SOLVENT INTEGRALS IN THE HERMIT SECTION, SEE CHAPTER .

.CTOCD

STARTS THE CALCULATION OF THE MAGNETIC PROPERTIES WITH THE CTOCD-DZ METHOD (REF. [,,]). THIS SETS ALSO AUTOMATICALLY THE .NOLOND OPTION SINCE THE CTOCD-DZ FORMALISM IS GAUGE INDEPENDENT FOR NUCLEAR MAGNETIC SHIELDINGS. THE DEFAULT GAUGE ORIGIN IS CHOOSEN TO BE THE CENTER OF MASS. .CTOCD AND .SOPPA OR .SOPPA(CCSD) CAN BE COMBINED TO PERFORM CTOCD CALCULATIONS AT THE SOPPA OR SOPPA(CCSD) LEVEL.

.DIPGRA

INVOKES THE CALCULATION OF DIPOLE MOMENT GRADIENTS (COMMONLY KNOWN ALSO AS ATOMIC POLAR TENSORS (APTS)) AS DESCRIBED IN REF. [149]. IF COMBINED WITH A REQUEST FOR .VIBANA THIS WILL GENERATE IR INTENSITIES.

.DIPORG

READ (LUCMD, *) (DIPORG(ICOOR), ICOOR = 1, 3)

READS IN A USER DEFINED DIPOLE ORIGIN. THIS MAY AFFECT PROPERTIES IN WHICH CHANGES IN THE DIPOLE ORIGIN IS CANCELED BY SIMILAR CHANGES IN THE NUCLEAR PART. IT SHOULD ALSO BE USED WITH CARE, AS THE SAME DIPOLE ORIGIN MUST BE USED DURING THE INTEGRAL EVALUATION SECTIONS, IN PARTICULAR IF ONE IS DOING NUMERICAL DIFFERENTIATION WITH RESPECT TO ELECTRIC FIELD PERTURBATIONS. FOR SUCH FINITE-FIELD CALCULATIONS, WE REFER TO CHAPTER , WHICH DEALS WITH FINITE FIELD CALCULATIONS. IT IS PRIMARILY USED FOR DEBUGGING.

.ECD

INVOKES THE CALCULATION OF ELECTRONIC CIRCULAR DICHROISM (ECD) AS DESCRIBED IN REF. [,]. THIS NECESSITATES THE SPECIFICATION OF THE NUMBER ELECTRONIC EXCITATIONS IN EACH SYMMETRY, GIVEN IN THE *EXCITA MODULE. THE READER IS REFERED TO THE SECTION WHERE THE CALCULATION OF ECD IS DESCRIBED IN MORE DETAIL (SEC. ).

.EXCITA

INVOKES THE CALCULATION OF ELECTRONIC EXCITATION ENERGIES AS RESIDUES OF LINEAR RESPONSE FUNCTIONS AS DESCRIBED BY OLSEN AND JøRGENSEN [47]. IT ALSO CALCULATES CLOSELY RELATED PROPERTIES LIKE TRANSITION MOMENTS AND ROTATORY STRENGTHS. COMBINED WITH THE KEYWORD .SOPPA OR .SOPPA(CCSD) IT INVOKES A SOPPA OR SOPPA(CCSD) CALCULATION OF ELECTRONIC EXCITATION ENERGIES AND TRANSITION MOMENTS.

.EXPFCK

INVOKES THE SIMULTANEOUS CALCULATION OF TWO-ELECTRON EXPECTATION VALUES AND DERIVATIVE FOCK-MATRICES. THIS IS DEFAULT IN DIRECT AND PARALLEL RUNS IN ORDER TO SAVE MEMORY. IN ORDINARY CALCULATIONS THE TOTAL CPU TIME WILL INCREASE AS A RESULT OF INVOKING THIS OPTION.

.EXPGRA

CALCULATES THE GRADIENT OF THE ORBITAL EXPONENTS. THIS CAN BE USED TO OPTIMIZE THE SO-CALLED POLARIZATION CONSISTENT BASIS SETS [] IF COMBINED WITH A SUITABLE SCRIPT FOR PREDICTING NEW ORBITAL EXPONENTS BASED ON THIS GRADIENT.

.GAUGEO

READ (LUCMD, *) (GAGORG(ICOOR), ICOOR = 1, 3)

READS IN A USER DEFINED GAUGE ORIGIN AND OVERWRITE BOTH THE .NOCMC OPTION, AS WELL AS THE DEFAULT VALUE OF CENTER-OF-MASS COORDINATES. NOTE THAT AN UNSYMMETRIC POSITION OF THE GAUGE ORIGIN WILL LEAD TO WRONG RESULTS IN CALCULATIONS EMPLOYING SYMMETRY, AS THE PROGRAM WILL NOT BE ABLE TO DETECT THAT SUCH A CHOICE OF GAUGE ORIGIN BREAKS THE SYMMETRY OF THE MOLECULE.

.HELLMA

TELLS THE PROGRAM TO USE THE HELLMAN-FEYNMAN APPROXIMATION WHEN CALCULATING THE MOLECULAR GRADIENTS AND HESSIANS [,,]--THAT IS, ALL CONTRIBUTIONS TO THE MOLECULAR GRADIENT AND HESSIANS FROM DIFFERENTIATION OF THE ORBITALS ARE IGNORED. REQUIRES LARGE BASIS SETS IN ORDER TO GIVE RELIABLE RESULTS, BUT DOES NOT REQUIRE ANY DIFFERENTIATED TWO-ELECTRON INTEGRALS.

.INPTES

CHECKS THE INPUT IN THE **PROPERTIES INPUT SECTION AND THEN STOPS.

.LINEAR

INVOKES THE LINEAR COUPLING MODEL FOR ESTIMATION OF FRANCK-CONDON FACTORS [153]. IN THIS MODEL, THE GRADIENT OF AN EXCITED STATE IS COMBINED WITH THE GROUND-STATE VIBRATIONAL FREQUENCIES AND NORMAL MODES TO PROVIDE VIBRONIC COUPLING CONSTANTS. REQUIRES THAT THE DALTON.HES FOR THE GROUND ELECTRONIC STATE IS AVAILABLE, AND THAT THE KEYWORD .VIBANA ALSO IS ACTIVATED.

.MAGNET

INVOKES THE CALCULATION OF THE MOLECULAR MAGNETIZABILITY (COMMONLY KNOWN AS MAGNETIC SUSCEPTIBILITY) AS DESCRIBED IN REF. [55] AND THE ROTATIONAL G TENSOR (SEE KEYWORD .MOLGFA). BY DEFAULT THIS IS DONE USING LONDON ORBITALS IN ORDER TO ENSURE FAST BASIS SET CONVERGENCE AS SHOWN IN REF. [55]. THE USE OF LONDON ORBITALS CAN BE DISABLED BY THE KEYWORD .NOLOND.

FURTHERMORE, THE NATURAL CONNECTION (REF. [,]) IS THE DEFAULT IN ORDER TO ENSURE NUMERICALLY STABLE RESULTS. THE NATURAL CONNECTION CAN BE TURNED OFF BY THE KEYWORD .NODIFC, IN WHICH CASE THE SYMMETRIC CONNECTION WILL BE USED.

THE GAUGE ORIGIN IS CHOSEN TO BE THE CENTER OF MASS OF THE MOLECULE. THIS ORIGIN CAN BE CHANGED BY THE TWO KEYWORDS .GAUGEO AND .NOCMC. THIS WILL OF COURSE NOT AFFECT THE TOTAL MAGNETIZABILITY, ONLY THE MAGNITUDE OF THE DIA- AND PARAMAGNETIC TERMS.

COMBINED WITH THE KEYWORD .SOPPA OR .SOPPA(CCSD) IT INVOKES A SOPPA OR SOPPA(CCSD) CALCULATION OF THE MAGNETIZABILITY AND THE ROTATIONAL G TENSOR (REF. [61]). LONDON ORBITALS ARE AUTOMATICALLY DISABLED IN SOPPA OR SOPPA(CCSD) CALCULATIONS.

.MAGNET IN COMBINATION WITH THE KEYWORD .CTOCD INVOKES A CALCULATION WITHOUT THE USE OF LONDON ORBITALS BOTH WITH THE CTOCD-DZ METHOD (REF [,]) AND WITH THE COMMON ORIGIN METHOD. CHANGING THE DEFAULT VALUE OF THE GAUGE ORIGIN COULD GIVE WRONG RESULTS!

.MOLGFA

INVOKES THE CALCULATION OF THE ROTATIONAL G TENSOR AS DESCRIBED IN REF. [73] AND THE MOLECULAR MAGNETIZABILITY (SEE KEYWORD .MAGNET). BY DEFAULT THIS IS DONE USING LONDON ORBITALS AND THE NATURAL CONNECTION. THE USE OF LONDON ORBITALS CAN BE TURNED OFF BY THE KEYWORD .NOLOND.

BY DEFINITION THE GAUGE ORIGIN OF THE MOLECULAR G-FACTOR IS TO BE THE CENTER OF MASS OF THE MOLECULE, AND ALTHOUGH THE GAUGE ORIGIN CAN BE CHANGED THROUGH THE KEYWORDS .NOCMC AND .GAUGEO, THIS IS NOT RECOMMENDED, AND MAY GIVE ERRONEOUS RESULTS.

NOTE THAT IF THE ISOTOPIC CONSTITUTION OF THE MOLECULE IS SUCH THAT THE VIBRATIONAL WAVE FUNCTION HAS LOWER SYMMETRY THAN THE ELECTRONIC WAVE FUNCTION, CARE MUST BE TAKEN TO ENSURE THE SYMMETRY CORRESPONDS TO THE SYMMETRY OF THE NUCLEAR FRAMEWORK. THE AUTOMATIC SYMMETRY DETECTION ROUTINES WILL IN GENERAL ENSURE THAT THIS IS THE CASE.

COMBINED WITH THE KEYWORD .SOPPA OR .SOPPA(CCSD) IT INVOKES A SOPPA OR SOPPA(CCSD) CALCULATION OF THE MAGNETIZABILITY AND THE ROTATIONAL G TENSOR (REF. [61]). LONDON ORBITALS ARE AUTOMATICALLY DISABLED IN SOPPA OR SOPPA(CCSD) CALCULATIONS.

.MOLGRA

INVOKES THE CALCULATION OF THE ANALYTICAL MOLECULAR GRADIENT AS DESCRIBED IN REF. [21].

.MOLHES

INVOKES THE CALCULATION OF THE ANALYTICAL MOLECULAR HESSIAN AND GRADIENT AS DESCRIBED IN REF. [21].

.NMR

INVOKES THE CALCULATION OF BOTH PARAMETERS ENTERING THE NMR SPIN-HAMILTONIAN, THAT IS NUCLEAR SHIELDINGS AND INDIRECT NUCLEAR SPIN-SPIN COUPLING CONSTANTS. THE READER IS REFERED TO THE DESCRIPTION OF THE TWO KEYWORDS .SHIELD AND .SPIN-S.

.NOCMC

THIS KEYWORD SETS THE GAUGE ORIGIN TO THE ORIGIN OF THE CARTESIAN COORDINATE SYSTEM, THAT IS (0,0,0). THIS KEYWORD IS AUTOMATICALLY INVOKED IN CASE OF VCD CALCULATIONS.

.NODARW

TURNS OFF THE CALCULATION OF THE DARWIN CORRECTION. BY DEFAULT THE TWO MAJOR RELATIVISTIC CORRECTIONS TO THE ENERGY IN THE BREIT-PAULI APPROXIMATION, THE MASS-VELOCITY AND DARWIN CORRECTIONS, ARE CALCULATED PERTURBATIVELY.

.NODIFC

DISABLES THE USE OF THE NATURAL CONNECTION, AND THE SYMMETRIC CONNECTION IS USED INSTEAD. THE NATURAL CONNECTION AND ITS DIFFERENCES AS COMPARED TO THE SYMMETRIC CONNECTION IS DESCRIBED IN REF. [,].

AS THE SYMMETRIC CONNECTION MAY GIVE NUMERICALLY INACCURATE RESULTS, IT'S USE IS NOT RECOMMENDED FOR OTHER THAN COMPARISONS WITH OTHER PROGRAMS.

.NOHESS

TURNS OFF THE CALCULATION OF THE ANALYTICAL MOLECULAR HESSIAN. THIS OPTION OVERRIDES ANY REQUEST FOR THE CALCULATION OF MOLECULAR HESSIANS.

.NOLOND

TURNS OFF THE USE OF LONDON ATOMIC ORBITALS IN THE CALCULATION OF MOLECULAR MAGNETIC PROPERTIES. THE GAUGE ORIGIN IS BY DEFAULT THEN CHOSEN TO BE THE CENTER OF MASS. THIS CAN BE ALTERED BY THE KEYWORDS .NOCMC AND .GAUGEO.

.NOMASV

TURNS OFF THE CALCULATION OF THE MASS-VELOCITY CORRECTION. BY DEFAULT THE TWO MAJOR RELATIVISTIC CORRECTIONS TO THE ENERGY IN THE BREIT-PAULI APPROXIMATION, THE MASS-VELOCITY AND DARWIN CORRECTIONS, ARE CALCULATED PERTURBATIVELY.

.NQCC

CALCULATES THE NUCLEAR QUADRUPOLE MOMENT COUPLING CONSTANTS.

.NUMHES

IN VROA OR RAMAN INTENSITY CALCULATIONS, USE THE NUMERICAL HESSIAN CALCULATED FROM THE ANALYTICAL GRADIENTS INSTEAD OF A FULLY ANALYTICAL MOLECULAR HESSIAN CALCULATION IN THE FINAL GEOMETRY.

.OPTROT

REQUESTS THE CALCULATION OF THE OPTICAL ROTATION OF A MOLECULE [,]. BY DEFAULT THE OPTICAL ROTATION IS CALCULATED BOTH WITH AND WITHOUT THE USE OF LONDON ORBITALS. NOTE THAT IN THE FORMALISM USED IN DALTON, THIS QUANTITY VANISHES IN THE STATIC LIMIT, AND FREQUENCIES NEED TO BE SET IN THE *ABALNR INPUT MODULE. SEE ALSO DESCRIPTION IN CHAPTER .

.PHASEO

READ (LUCMD, *) (ORIGIN(ICOOR), ICOOR = 1, 3)

CHANGES THE ORIGIN OF THE PHASE-FACTORS ENTERING THE LONDON ATOMIC ORBITALS. THIS WILL CHANGE THE VALUE OF ALL OF THE CONTRIBUTIONS TO THE DIFFERENT MAGNETIC FIELD DEPENDENT PROPERTIES WHEN USING LONDON ATOMIC ORBITALS, BUT THE TOTAL MAGNETIC PROPERTIES WILL REMAIN UNCHANGED. TO BE USED FOR DEBUGGING PURPOSES ONLY.

.POLARI

INVOKES THE CALCULATION OF FREQUENCY-INDEPENDENT POLARIZABILITIES. SEE THE KEYWORD .ALPHA IN THIS INPUT SECTION FOR THE CALCULATION OF FREQUENCY-DEPENDENT POLARIZABILITIES.

.POPANA

INVOKES A POPULATION ANALYSIS BASED ON THE DIPOLE GRADIENT AS FIRST INTRODUCED BY CIOSLOWSKI [38]. THIS FLAG ALSO INVOKES THE .DIPGRA FLAG AND THE .POLARI FLAGS. NOTE THAT THE CHARGES OBTAINED IN THIS APPROACH IS NOT WITHOUT CONCEPTUAL PROBLEMS (AS ARE THE MULLIKEN CHARGES) [].

.PRINT

READ (LUCMD, *) IPRDEF

SET DEFAULT PRINT LEVEL FOR THE CALCULATION. READ ONE MORE LINE CONTAINING PRINT LEVEL. DEFAULT PRINT LEVEL IS THE VALUE OF IPRDEF FROM THE GENERAL INPUT MODULE.

.QUADRU

CALCULATES THE MOLECULAR QUADRUPOLE MOMENT. THIS INCLUDES BOTH THE ELECTRONIC AND NUCLEAR CONTRIBUTION TO THE QUADRUPOLE MOMENT. THESE WILL PRINTED SEPARATELY ONLY IF A PRINTED LEVEL OF 2 OR HIGHER HAS BEEN CHOSEN. NOTE THAT THE QUADRUPOLE MOMENT IS DEFINED ACCORDING TO BUCKINGHAM [42]. THE QUADRUPOLE MOMENT IS PRINTED IN THE MOLECULAR INPUT ORIENTATION AS WELL AS BEING TRANSFORMED TO THE PRINCIPAL MOMENTS OF INERTIA COORDINATE SYSTEM.

.RAMAN

CALCULATES RAMAN INTENSITIES, AS DESCRIBED IN REF. [41]. THIS PROPERTY NEEDS A LOT OF SETTINGS IN ORDER TO PERFORM CORRECTLY, AND THE READER IS THEREFORE REFERED TO SECTION , WHERE THE CALCULATION OF THIS PROPERTY IS DESCRIBED IN MORE DETAIL.

.REPS

READ (LUCMD, *) NREPS
READ (LUCMD, *) (IDOSYM(I),I = 1, NREPS)

CONSIDER PERTURBATIONS OF SELECTED SYMMETRIES ONLY. READ ONE MORE LINE SPECIFYING HOW MANY SYMMETRIES, THEN ONE LINE LISTING THE DESIRED SYMMETRIES. THIS OPTION IS CURRENTLY ONLY IMPLEMENTED FOR GEOMETRIC PERTURBATIONS.

.SELECT

READ (LUCMD,*) NPERT
READ (LUCMD, *) (IPOINT(I),I=1,NPERT)

SELECT WHICH NUCLEAR GEOMETRIC PERTURBATIONS ARE TO BE CONSIDERED. READ ONE MORE LINE SPECIFYING HOW MANY PERTURBATIONS, THEN ON A NEW LINE THE LIST OF PERTURBATIONS TO BE CONSIDERED. BY DEFAULT, ALL PERTURBATIONS ARE TO BE CONSIDERED, BUT BY INVOKING THIS KEYWORD, ONLY THOSE PERTURBATIONS SPECIFIED IN THE SEQUENCE WILL BE CONSIDERED.

THE PERTURBATION ORDERING FOLLOWS THE ORDERING OF THE SYMMETRIZED NUCLEAR COORDINATES. THIS ORDERING CAN BE OBTAINED BY SETTING THE PRINT LEVEL IN THE *READIN MODULE TO 20 OR HIGHER.

.SHIELD

INVOKES THE CALCULATION OF NUCLEAR SHIELDING CONSTANTS. BY DEFAULT THIS IS DONE USING LONDON ORBITALS IN ORDER TO ENSURE FAST BASIS SET CONVERGENCE AS SHOWN IN REF. [,]. THE USE OF LONDON ORBITALS CAN BE DISABLED BY THE KEYWORD .NOLOND.

FURTHERMORE, THE NATURAL CONNECTION (REF. [,]) IS THE DEFAULT IN ORDER TO ENSURE NUMERICALLY STABLE RESULTS AS WELL AS PHYSICALLY INTERPRETABLE RESULTS FOR THE PARAMAGNETIC AND DIAMAGNETIC TERMS. THE NATURAL CONNECTION CAN BE TURNED OFF BY THE KEYWORD .NODIFC IN WHICH CASE THE SYMMETRIC CONNECTION IS USED INSTEAD.

THE GAUGE ORIGIN IS CHOSEN TO BE THE CENTER OF MASS OF THE MOLECULE. THIS ORIGIN CAN BE CHANGED BY THE TWO KEYWORDS .GAUGEO AND .NOCMC . THIS CHOICE OF GAUGE ORIGIN WILL NOT AFFECT THE FINAL SHIELDINGS IF LONDON ORBITALS ARE USED, ONLY THE SIZE OF THE DIA- AND PARAMAGNETIC CONTRIBUTIONS.

COMBINED WITH THE KEYWORD .SOPPA OR .SOPPA(CCSD) IT INVOKES A SOPPA OR SOPPA(CCSD) CALCULATION OF THE NUCLEAR MAGNETIC SHIELDINGS (REF. [,,]). LONDON ORBITALS ARE AUTOMATICALLY DISABLED IN SOPPA OR SOPPA(CCSD) CALCULATIONS. GAUGE ORIGIN INDEPENDENT SOPPA OR SOPPA(CCSD) CALCULATIONS OF NUCLEAR MAGNETIC SHIELDINGS CAN BE CARRIED OUT WITH THE CTOCD-DZ METHOD (SEE REFS. [,,]) USING THE KEYWORD .CTOCD.

IN COMBINATION WITH THE KEYWORD .CTOCD THIS INVOKES A CALCULATION OF THE NUCLEAR MAGNETIC SHIELDINGS WITHOUT THE USE OF LONDON ORBITALS BUT WITH BOTH THE CTOCD-DZ METHOD (REF. [,,]) AND WITH THE COMMON ORIGIN METHOD. FOR THE CTOCD-DZ METHOD THE NUCLEAR MAGNETIC SHIELDINGS ARE GIVEN IN THE OUTPUT FILE FOR BOTH THE ORIGIN AT THE CENTER OF MASS AND AT THE RESPECTIVE ATOMS. CHANGING THE DEFAULT VALUE OF THE GAUGE ORIGIN COULD GIVE WRONG RESULTS!

.SOPPA

INDICATES THAT THE REQUESTED MOLECULAR PROPERTIES BE CALCULATED USING THE SECOND-ORDER POLARIZATION-PROPAGATOR APPROXIMATION [50]. THIS REQUIRES THAT THE MP2 ENERGY AND WAVE FUNCTION HAVE BEEN CALCULATED. LONDON ORBITALS CAN NOT BE USED TOGETHER WITH THE SOPPA APPROXIMATION.

.SOPPA(CCSD)

INDICATES THAT THE REQUESTED MOLECULAR PROPERTIES BE CALCULATED USING THE SECOND-ORDER POLARIZATION-PROPAGATOR APPROXIMATION WITH COUPLED CLUSTER SINGLES AND DOUBLES AMPLITUDES [,,,]. THIS REQUIRES THAT THE CCSD ENERGY AND WAVE FUNCTION HAVE BEEN CALCULATED. LONDON ORBITALS CAN NOT BE USED TOGETHER WITH THE SOPPA(CCSD) APPROXIMATION.

.SPIN-R

INVOKES THE CALCULATION OF SPIN-ROTATION CONSTANTS AS DESCRIBED IN REF. [73]. BY DEFAULT THIS IS DONE USING LONDON ORBITALS AND THE NATURAL CONNECTION. THE USE OF LONDON ORBITALS CAN BE TURNED OFF BY THE KEYWORD .NOLOND.

BY DEFINITION THE GAUGE ORIGIN OF THE SPIN-ROTATION CONSTANT IS TO BE THE CENTER OF MASS OF THE MOLECULE, AND ALTHOUGH THE GAUGE ORIGIN CAN BE CHANGED THROUGH THE KEYWORDS .NOCMC AND .GAUGEO, THIS IS NOT RECOMMENDED, AND MAY GIVE ERRONEOUS RESULTS.

IN THE CURRENT IMPLEMENTATION, SYMMETRY DEPENDENT NUCLEI CANNOT BE USED DURING THE CALCULATION OF SPIN-ROTATION CONSTANTS.

.SPIN-S

INVOKES THE CALCULATION OF INDIRECT NUCLEAR SPIN-SPIN COUPLING CONSTANTS. BY DEFAULT ALL SPIN-SPIN COUPLINGS BETWEEN NUCLEI WITH NATURALLY OCCURING ISOTOPES WITH ABUNDANCE MORE THAN 1% AND NON-ZERO SPIN WILL BE CALCULATED, AS WELL AS ALL THE DIFFERENT CONTRIBUTIONS (FERMI CONTACT, DIA- AND PARAMAGNETIC SPIN-ORBIT AND SPIN-DIPOLE). THE IMPLEMENTATION IS DESCRIBED IN REF. [60].

AS THIS IS A VERY TIME CONSUMING PROPERTY, IT IS RECOMMENDED TO CONSULT THE CHAPTER DESCRIBING THE CALCULATION OF NMR-PARAMETERS (CH. ). THE MAIN CONTROL OF WHICH CONTRIBUTIONS AND WHICH NUCLEI TO CALCULATE SPIN-SPIN COUPLINGS BETWEEN IS DONE IN THE *SPIN-S MODULE.

.VCD

INVOKES THE CALCULATION OF VIBRATIONAL CIRCULAR DICHROISM (VCD) ACCORDING TO THE IMPLEMENTATION DESCRIBED IN REF. [77]. BY DEFAULT THIS IS DONE USING LONDON ORBITALS IN ORDER TO ENSURE FAST BASIS SET CONVERGENCE AS SHOWN IN REF. [82]. THE USE OF LONDON ORBITALS CAN BE DISABLED BY THE KEYWORD .NOLOND.

FURTHERMORE, THE NATURAL CONNECTION (REF. [,]) IS DEFAULT IN ORDER TO ENSURE NUMERICALLY STABLE RESULTS. THE NATURAL CONNECTION CAN BE TURNED OFF BY THE KEYWORD .NODIFC IN WHICH CASE THE SYMMETRIC CONNECTION WILL BE USED.

IN THE CURRENT IMPLEMENTATION, THE KEYWORD .NOCMC WILL BE SET TRUE IN CALCULATIONS OF VIBRATIONAL CIRCULAR DICHROISM, THAT IS, THE COORDINATE SYSTEM ORIGIN WILL BE USED AS GAUGE ORIGIN. CHANGING THIS DEFAULT VALUE WILL GIVE INCORRECT RESULTS FOR VCD.

NOTE THAT IN THE CURRENT RELEASE, VCD IS NOT IMPLEMENTED FOR DENSITY FUNCTIONAL THEORY CALCULATIONS, AND THE PROGRAM WILL STOP IF VCD IS REQUESTED FOR A DFT CALCULATION.

.VIBANA

INVOKES A VIBRATIONAL ANALYSIS IN THE CURRENT GEOMETRY. THIS WILL GENERATE THE VIBRATIONAL FREQUENCIES IN THE CURRENT POINT. IF COMBINED WITH .DIPGRA THE IR INTENSITIES WILL BE CALCULATED AS WELL.

.VROA

INVOKES THE CALCULATION OF VIBRATIONAL RAMAN OPTICAL ACTIVITY, AS DESCRIBED IN REF. [41]. THIS PROPERTY NEEDS A LOT OF SETTINGS IN ORDER TO PERFORM CORRECTLY, AND THE READER IS THEREFORE REFERED TO SECTION , WHERE THE CALCULATION OF THIS PROPERTY IS DESCRIBED IN MORE DETAIL.

.WRTINT

FORCES THE MAGNETIC FIRST-DERIVATE TWO-ELECTRON INTEGRALS TO BE WRITTEN TO DISC. THIS IS DEFAULT IN MCSCF CALCULATIONS, BUT NOT FOR SCF RUNS. THIS FILE CAN BE VERY LARGE, AND IT IS NOT RECOMMENDED TO USE THIS OPTION FOR ORDINARY SCF RUNS.