Franck-Condon calculations

FCON,options [fcon]

The FCON program allows for the calculation of Franck-Condon factors based on potential energy surfaces obtained from the XSURF program and vibrational wavefunctions as provided by the VSCF or VCI programs. Duschinsky effects may or may not be included. These can either be applied to the vibrational wavefunction (of the vibrational ground state) or the potential by using the PESTRANS program. The latter possibility is the recommended one as it is significantly faster. The FCON program including Duschinsky rotations can only be used with analytical representations of the potential energy surfaces. A prescreening of the Franck-Condon factors without Duschinsky effects at the VSCF level is used to reduce the computational effort for correlated levels, e.g. VCI. Note that, Franck-Condon factors at the uncorrelated VSCF level including Duschinsky effects are usually of fairly poor quality. As the calculation of Franck-Condon factors often involves very high quantum numbers for the vibrational states of the final electronic state, very high excitation levels must be enabled in the VCI calculations, i.e. see keyword LEVEX. For details see:
P. Meier, G. Rauhut, Comparison of methods for calculating Franck-Condon factors beyond the harmonic approximation: how important are Duschinsky rotations?, Mol. Phys. 113, 3859 (2015).
G. Rauhut, Anharmonic Franck-Condon factors for the $\tilde{\mbox{X}}\,{}^2$B${}_1 \longleftarrow \tilde{\mbox{X}}\,{}^1$A${}_1$ photoionization of ketene, J. Phys. Chem. A 119, (2015) 10264.

The following options are available:

• DUSCH=n This keyword controls the Duschinsky transformation. DUSCH=0 entirely neglects the Duschinsky transformation - including the shift-vector. DUSCH=3 neglects the Duschinsky rotation, but includes the shift-vector. This is the default option as the Duschinsky rotation can be passed to the PESTRANS program, which is much more efficient.
• ECKART=n ECKART=1 (default) determines the Eckart transformation matrix as described in the literature. ECKART=0 approximates the Eckart transformation matrix by a unit matrix, which is meaningless unless for debugging purposes or for some very special tests.
• MAXSEL=n MAXSEL=n determines the maximum number of Franck-Condon factors to be selected. By default n is set to 100.
• SEL=n This option switches the selection of Franck-Condon factors based on VSCF calculation on (SEL=1) or off (SEL=0, default).
• THRDELTA=value The $\delta$-criterion is a threshold, which allows for the prescreening of overlap integrals within the evaluation of the Franck-Condon factors prior to their evaluation. The default is set to 1.0d-8.
• THRFCF=value The sum of all Franck-Condon factors is 1.0d0 by definition. However, this value is hard to reach by sum over states approaches. Therefore, it can be lowered by this keyword.
• THRFCFSPEC=value This threshold controls, if a Franck-Condon factor will be considered within the plotting of the spectrum. See the PUT command and the IRSPEC style. The default is 1.0d-6.
• THRPRINT=value This keyword defines the smallest value of a Franck-Condon factor to be printed in the output. The default is set to 1.0d-99, i.e. this threshold usually is inactive.
• THRSEL=value This threshold controls, if a Franck-Condon factor shall be selected and thus be considered in all subsequent calculations or not. The default is 1.0d-5.
• THRSKIPBAS=value Basis functions in the outer regions of the potentials may be skipped within the calculation of Franck-Condon factors. In particular within the approach of Doktorov, the CPU time depends strongly on the number of basis functions. This keyword allows to skip such basis functions and is given as the overlap integral of the modal. The default is 0.999999d0.
• THRSUMSEL=value This threshold controls the sum of the selected Franck-Condon factors, which must formally be 1.0d0. The default is set to 0.999999d0.
• THRVCIMIN=value Within the calculation of Franck-Condon factors based on VCI wavefunctions, the leading VCI coefficient should be largest in order to correspond to the state of interest. The default is set to 0.01d0, which of course means that this keyword essentially is inactive.
• WF=type Defines the type of the wavefunction. WF=VSCF specifies state-specific VSCF wavefunctions for both levels, while WF=VCI denotes state-specific VCI wavefunctions. Alternatively, one may use WF=VSCFG for ground-state based VSCF wavefunctions and WF=VCIG for ground-state based VCI wavefunctions. The default is WF=VCI.

Some of the keywords as described for the VCI program are also valid for the FCON program, i.e. CITYPE, LEVEX, CIMAX, NDIM, NBAS, BASIS and INFO.

DISK,options
As the Franck-Condon program requests the information of two sets of potentials and wave functions, the information handling is controlled by an extra directive. All the records provided here must refer to the defaults or the explicitly given records in the preceding POLY, VSCF and VCI calculations.

• FINAL=n Rather than specifying the records explicitly, the number of the final state as defined in DISK directive of the POLY program may be used.
• INITIAL=n Rather than specifying the records explicitly, the number of the initial state as defined in DISK directive of the POLY program may be used.
• SURF1=record Specifies the record from where to read the potential information for the final PES.
• SURF2=record Specifies the record from where to read the potential information for the initial PES.
• VSCF1=record Specifies the record from where to read the VSCF information for the final wave function.
• VSCF2=record Specifies the record from where to read the VSCF information for the initial wave function.
• VCI1=record Specifies the record from where to read the VCI information for the final wave function.
• VCI2=record Specifies the record from where to read the VCI information for the initial wave function.

The following example shows the input for a calculation of Franck-Condon factors at the VCI level. The selection of important Franck-Condon factors will be done at the VSCF level without Duschinsky rotation.

memory,20,m
basis=vdz
orient,mass
geometry={
   3
Water
O          0.0675762564        0.0000000000       -1.3259214590
H         -0.4362118830       -0.7612267436       -1.7014971211
H         -0.4362118830        0.7612267436       -1.7014971211
}

label1
hf

{xsurf,sym=auto                    ! read in the PES of the initial electronic state and assign it to surface label 1
 disk,where=home,auto=1,extern='final.pot'}
    
{poly
 disk,auto=1}                      ! read surface 1 from disk and transform it to polynomials
{vscf,pot=poly                     
 disk,auto=1}                      ! read polynomials for surface 1 from disk and perform a VSCF calculation 
    
{xsurf,sym=auto                    ! read in the PES of the final electronic state and assign it to surface label 2
  disk,where=home,auto=2,extern='initial.pot'}       
    
{poly
 disk,auto=2}                      ! read surface 2 from disk and transform it to polynomials
{vscf,pot=poly
 disk,auto=2}                      ! read polynomials for surface 2 from disk and perform a VSCF calculation
 
{fcon,wf=vscfg,sel=1               ! perform a Franck-Condon calculation at the VSCF level in order to
 disk,initial=2,final=1}           ! identify important transitions, which shall be considered later in the VCI part
 
{poly,vam=0                        ! transform PES 2 to polynomials without adding the Watson correction term
 disk,auto=2}                      ! as a pseudopotential to (this is needed for the subsequent transformation)
 
{pestrans,transtype=fcf,umat=1     ! transform PES 2 (initial) to the axes (normal coordinates) of PES 1 (final state)
 disk,where=home,auto=2            ! (Duschinsky transformation)
 disk,extern='initial.pot'}                  
                                         
{poly                              ! transform the transformed PES to polynomials       
 disk,auto=2}
{vscf,pot=poly                     ! do a VSCF calculation for surface 2
 disk,auto=2}                           
{vci,pot=poly,export=fcon          ! perform a VCI calculation for surface 2 and export the VCI vectors for     
 disk,auto=2}                      ! the Franck-Condon program     
                                         
{poly                              ! transform surface 1 to polynomials   
 disk,auto=1}                           
{vscf,pot=poly                     ! perform a VSCF calculation for surface 1              
 disk,auto=1}                             
{vci,pot=poly,export=fcon          ! perform a VCI calculation for surface 1 and export the VCI vectors for 
 disk,auto=1}                      ! the Franck-Condon program
 
{fcon                              ! perform a Franck-Condon calculation on the basis of the selected VCI states
 disk,initial=2,final=1}

put,irspec,h2o_pe.gnu              ! generate a GNU file with the PE spectrum

EVSPEC,options [evspec]

Similar to the FCON, the EVSPEC program allows for the calculation of anharmonic electronic-vibrational absorption spectra with the inclusion of Duschinsky effects. In addion, it can take finite-temperature effects into account as arising from the thermal population of the excited vibrational levels of the electronic ground PES. The program requires a precalculated set of initial VCI wavefuncions, a polynomial representation of the final PES, and the corresponding VSCF ground-state modals. In addition, the initial VCI states should be provided in the same set of normal coordinates as the final PES, which is achieved by the coordinate transformation of the potential energy function via the PESTRANS program. All these aspect will be illustrated in the examples below.

There are basically two approaches employed in this module. The first one consists in the determination of the eigenstates with the largest Franck-Condon factors within the formalism of contracted invariant Krylov subspaces (CIKS) by means of the Lanczos or RACE methods. Alternatively, the specta can be evaluated using the time-independent eigenstate-free ansatz based on the inhomogeneous Schrödinger equation. The solution of this equation, the so-called Raman wavefunction (RWF), is directly related to the spectral intensities. For details see:
T. Petrenko, G. Rauhut, Time-independent eigenstate-free calculation of vibronic spectra beyond the harmonic approximation , J. Chem. Phys. 143, 234106 (2015).
T. Petrenko, G. Rauhut, A new efficient method for the calculation of interior eigenpairs and its application to vibrational structure problems , J. Chem. Phys. 146, 124101 (2017).
T. Petrenko, G. Rauhut, A general approach for calculating strongly anharmonic vibronic spectra with a high density of states: the $\tilde{\mbox{X}}\,{}^2$B${}_1 \longleftarrow \tilde{\mbox{X}}\,{}^1$A${}_1$ photoelectron spectrum of difluoromethane, J. Chem. Theory Comput. 13, 5515 (2017).
T. Petrenko, G. Rauhut, Refined analysis of the $\tilde{\mbox{X}}\,{}^2$A${}_2 \longleftarrow \tilde{\mbox{X}}\,{}^1$A${}_1$ photoelectron spectrum of furan , J. Chem. Phys. 148, 054306 (2018).

The following options are available:

• METHOD=CIKS|RWF Defines the method of calculation. METHOD=CIKS specifies the CIKS approach which enables the determination of the eigenstates with the most significant Franck-Condon factors. METHOD=RWF denotes the eigenstate-free method based on the Raman wavefunction formalism.
  

Default: METHOD=RWF.

• INITIAL=n1, FINAL=n2
  

These keywords provide the reference values for the initial and final PESs, respectively. In this case, the option AUTO=n1 within the DISK directive of the POLY, VSCF, or VCI blocks would attribute the respective computational results to the initial PES, while AUTO=n2 would attribute them to the final PES.
Default: INITIAL=1, FINAL=2.

The keyword INFO has the same meaning as in the other programs.

ISTATES,options
For a given temperature, the program can calculate the spectrum with the contributions from all initial states which are found in the VCI record. This directive provides the opportunity to control the prescreening of the initial states based on their relative thermal populations. The following options are possible:

• TEMPK=value Provides the temperature in Kelvin.
  

Default: TEMPK=300.0.

• THRPOP=value The initial states with the relative thermal populations (with respect to the ground vibrational level) which are below this parameter will be neglected.
  

Default: THRPOP=1.0d-3.

RWF,options
This directive provides various computational settings which are specific to the RWF calculations. Currently, only the iterative subspace algoritm of Lanczos type is impemented. The following options are possible:

• ERANGE=value1,value2 Defines the spectral range in 1/cm unit for the RWF calculation relative to the 0-0 trasnition energy. In the case that the eV unit is implied, see the explanation for the keyword EUNIT.
  

Default: automatic determination of the spectral range with significant intensity.

• EUNIT=CM|EV Defines the energy unit for the values specified via the keywords ERANGE and GAMMA. CM and EV stand for 1/cm and eV, respectively.
  

Default: EUNIT=CM.

• GAMMA=value Defines the damping factor in 1/cm unit. In the case that the eV unit is implied, see the explanation for the keyword EUNIT.
  

Default: GAMMA=100.0.

• NLMAX=n Defines the maximum number of Lanczos iterations.
  

Default: NLMAX=2000.

• NSMAX=n Defines the maximum number of printed approximate eigenstates representing the RWF.
  

Default: NSMAX=2000.

• THRCONV=value Defines the convergence threshold for the RWF in terms of the dimensionless squared residual norm for the inhomogeneous Schrödinger equation.
  

Default: THRCONV=1.0d-3.

• THRFCF=value This is the threshold for the sum of the FCFs which controls the number of printed approximate eigenstates representing the RWF.
  

Default: THRFCF=0.999.

CIKS,options
This directive provides the computational settings that are specific to the CIKS calculations. The following options are possible:

• METHOD=LCS|RACE Defines the method of calculation. Currently, two choices are possible: Lanczos (LCS) and RACE (RACE) algorithms.
  

Default: METHOD=RACE.

• NDMAX=n Defines the maximum number of the state-specific expansion vectors. It is valid only for METHOD=RACE.
  

Default: NDMAX=1000.

• NEVMAX=n Defines the maximum number of the eigenvectors to be calculated in one batch (NEVMAX$\leq$NSMAX).
  

Default: NEVMAX=20 for the RACE method, and NEVMAX=NLMAX for the Lanczos one.

• NLMAX=n Defines the maximum number of Lanczos iterations.
  

Default: NLMAX=2000 for the Lanczos method, and NLMAX=300 for the RACE one.

• NSMAX=n Defines the maximum number of the eigenstates to be calculated. The same number of states will be printed out.
  

Default: NSMAX=100 for the RACE method, and NSMAX=NLMAX for the Lanczos one.

• THREN=value Defines the convergence threshold for the calculated eigenstates in terms of the residual norm in Hartree unit.
  

Default: THREN=1.0d-7.

• THRFCF=value This is the threshold for the sum of the FCFs which additionally controls the total number of the calculated and printed eigenstates.
  

Default: THRFCF=0.999.

VCIBASIS,options
This directive controls the choice of the vibrational configuration basis. The following options are possible:

• REFTYPE=n Controls the selection of the reference configuration involved in the generation of the VCI basis. REFTYPE=1 refers to the ground vibrational configuration. The other choices are based on the calculated modal-contracted Franck-Condon factors (MCFCFs). For REFTYPE=2, the modals with the largest MCFCF is selected for the respective components of the reference vector, while for REFTYPE=3, one takes the modal which approximately corresponds to the average of the MCFCF distribution over the modals.
  

Default: REFTYPE=3.

The keywords CITYPE, LEVEX, and CIMAX restrict the VCI basis to certain excitation patterns, and have the same meaning as in the other modules:

• CIMAX=n Defines the maximum total excitation level over all modes.
  

Default: CIMAX=6.

• CITYPE=n Defines the maximum number of simultaneously excited modes relative to the reference configuration.
  

Default: CITYPE=4.

• LEVEX=n Defines the maximum excitation level within a single mode.
  

Default: LEVEX=4.

HMAT,options
This directive controls the construction of the VCI Hamiltonian matrix. The following options are possible:

• THRSPARSE=value Defines the threshold for neglecting the off-diagonal elements in the Hamiltonian matrix stored in a packed sparse form. The smaller is this value the higher are the memory demands, and the computational cost of the matrix-vector multiplications. In particular, setting THRSPARSE=0.0 would not lead to any meaningful changes in the calculated transition energies and intensities, but can easily increase the memory demands by $\sim 10-10000$ times as compared to the default value.
  

Default: THRSPARSE=1.0d-6.

GRAPH,options
This directive controls the output of the calculated spectra for plotting with the GNUPLOT program. Thus far, a single option is available:

• EVSDUMP=file name Provides the name of the gnuplot input file.
  

Default: EVSDUMP=’InputFileName.evs.gnu’.

The following example shows a general program flow involving the EVSPEC calculations.

memory,40,m

basis=vdz
geometry={
H   ,,     2.3971901752  ,    -2.3962403391   ,    0.0000000000
S   ,,    -0.0873406755  ,    -1.8178592700   ,    0.0000000000
S   ,,     0.0117763411  ,     1.8933936636   ,    0.0000000000
}

basis=vdz
hf

{xsurf                                            ! reads the PES of the initial electronic
 disk,where=home,extern='initial.pot'}            ! state from 'initial.pot'

poly                                              ! Transform  the initial PES to the
vscf,pot=poly                                     ! representation in terms of the normal
vci,pot=poly                                      ! coordinates of the final PES
                                                  ! (stored in 'final.pot'), and fit it
{pestrans,info=1                                  ! with polynomial functions.
 disk,where=home,auto=1,extern='final.pot'}       ! All results for the initial surface
                                                  ! are stored with the reference number
{poly                                             ! given by the keyword auto=1.
 disk,auto=1}
{vscf,pot=poly                                    ! Run VSCF calculations for initial states.
 disk,auto=1}                                     
{vci,pot=poly,export='EVSPEC'                     ! Run VCI calculations for initial states.
 disk,auto=1}

{xsurf                                            ! Reads the PES of the final electronic
 disk,where=home,auto=2,extern='final.pot'}       ! state from 'final.pot'.

{poly                                             ! Provides the polynomial representation
 disk,auto=2}                                     ! of the final PES.
{vscf,pot=poly                                    ! Run VSCF calculations for generating
 disk,auto=2}                                     ! vibrational modals for the final PES.

{evspec,method=rwf,start=1,final=2,info=1         ! Simple input for the RWF calculation
graph, evsdump='hs2_rwf.gnu'}