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| vibration_correlation_programs [2025/01/24 09:55] – rauhut | vibration_correlation_programs [2025/05/22 14:03] (current) – rauhut |
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| * **''NDIMDIP''=//n//** Term after which the $n$-body expansions of the dipole surfaces are truncated. The default is set to 3. Note that ''NDIMDIP'' has to be lower or equal to ''NDIM''. | * **''NDIMDIP''=//n//** Term after which the $n$-body expansions of the dipole surfaces are truncated. The default is set to 3. Note that ''NDIMDIP'' has to be lower or equal to ''NDIM''. |
| * **''NDIMPOL''=//n//** Term after which the $n$-body expansions of the polarizability tensor surfaces are truncated. The default is set to 0. Note that ''NDIMPOL'' has to be lower or equal to ''NDIM''. | * **''NDIMPOL''=//n//** Term after which the $n$-body expansions of the polarizability tensor surfaces are truncated. The default is set to 0. Note that ''NDIMPOL'' has to be lower or equal to ''NDIM''. |
| | * **''NDIMQUAD''=//n//** Term after which the $n$-body expansions of the quadrupole tensor surfaces are truncated. The default is set to 0. Note that ''NDIMQUAD'' has to be lower or equal to ''NDIM''. |
| * **''NSTSEL''=//n//** (=0 (off) Default) Once switched on (''NSTSEL=1'') the configuration selection procedure acts on several states simultaneously. The number and identity of these states will be automatically determined. Be aware, that this option leads to a significant increase of CPU time due to enlarged correlation spaces. | * **''NSTSEL''=//n//** (=0 (off) Default) Once switched on (''NSTSEL=1'') the configuration selection procedure acts on several states simultaneously. The number and identity of these states will be automatically determined. Be aware, that this option leads to a significant increase of CPU time due to enlarged correlation spaces. |
| * **''PRINT''=//n//** This option provides an extended output. ''PRINT=1'' prints the vibrationally averaged rotational constants for all computed states and the associated vibration-rotation constants $\alpha$. ''PRINT=2'' prints the effective 1D polynomials in case that the potential is represented in terms of polynomials, see the option ''POT=POLY'' and the ''POLY'' program. In addition the generalized VSCF property integrals, i.e. $\left < VSCF \left | q_i^r \right | VSCF \right >$ are printed. These integrals allow for the calculation of arbitrary vibrationally averaged properties once the property surfaces are available. Default: ''PRINT=0''. | * **''PRINT''=//n//** This option provides an extended output. ''PRINT=1'' prints the vibrationally averaged rotational constants for all computed states and the associated vibration-rotation constants $\alpha$. ''PRINT=2'' prints the effective 1D polynomials in case that the potential is represented in terms of polynomials, see the option ''POT=POLY'' and the ''POLY'' program. In addition the generalized VSCF property integrals, i.e. $\left < VSCF \left | q_i^r \right | VSCF \right >$ are printed. These integrals allow for the calculation of arbitrary vibrationally averaged properties once the property surfaces are available. Default: ''PRINT=0''. |
| * **''DUMP_IR''=//string//** File name for dumping the rovibrational infrared line list. Activates calculation of rovibrational intensities. | * **''DUMP_IR''=//string//** File name for dumping the rovibrational infrared line list. Activates calculation of rovibrational intensities. |
| * **''DUMP_PFIT''=//string//** File name for dumping the term energies for the fitted spectroscopic parameters. | * **''DUMP_PFIT''=//string//** File name for dumping the term energies for the fitted spectroscopic parameters. |
| | * **''DUMP_QUAD''=//string//** File name for dumping the line list for quadrupole transitions. Activates calculation of rovibrational intensities. |
| * **''DUMP_RAMAN''=//string//** File name for dumping the rovibrational Raman line list. Activates calculation of rovibrational intensities. | * **''DUMP_RAMAN''=//string//** File name for dumping the rovibrational Raman line list. Activates calculation of rovibrational intensities. |
| * **''HOTB''=//n//** (=0 (off) Default) The calculation of vibrational hot bands can be switched on with ''HOTB=1''. | * **''HOTB''=//n//** (=0 (off) Default) The calculation of vibrational hot bands can be switched on with ''HOTB=1''. |
| * **''INFO''=//n//** (=1 Default) Additional rovibrational output. By default this will print the nuclear spin statistical weights. ''INFO=2'' provides additional details on the calculation and assignment of nuclear spin statstical weights. ''INFO=3'' enables further integrals, etc. | * **''INFO''=//n//** (=1 Default) Additional rovibrational output. By default this will print the nuclear spin statistical weights. ''INFO=2'' provides additional details on the calculation and assignment of nuclear spin statstical weights. ''INFO=3'' enables further integrals, etc. |
| * **''IRUNIT''=//string//** The default unit for the IR intensities in HITRAN units, i.e. cm$^{-1}$/(molecule cm$^{-2}$). Alternatively, one may use ''IRUNIT=KMMOL'' to specify km/mol. | * **''IRUNIT''=//string//** The default unit for the IR intensities in HITRAN units, i.e. cm$^{-1}$/(molecule cm$^{-2}$). Alternatively, one may use ''IRUNIT=KMMOL'' to specify km/mol. |
| * **''JMAX''=//n//** By default VCI calculations will be performed for non-rotating molecules, i.e. ''J=0''. Rovibrational levels can be computed for arbitrary numbers of ''J$=n$''. This will perform a purely rotational calculation (RCI). To obtain approximate rovibrational energies, vibrational energies have to be added. | * **''JMAX''=//n//** By default VCI calculations will be performed for non-rotating molecules, i.e. ''J=0''. Rovibrational levels can be computed for arbitrary numbers of ''J$=n$''. This keyword is not mandatory as a default for ''JMAX'' will be determined from the partition function. |
| * **''JMAX_PRINT''=//n//** (=3 Default for ''JMAX''>3) This option controls the printout in rovibrational calculations, i.e. the maximum J value, up to which information shall be printed. | * **''JMAX_PRINT''=//n//** (=3 Default for ''JMAX''>3) This option controls the printout in rovibrational calculations, i.e. the maximum J value, up to which information shall be printed. |
| * **''LLPRINT''=//n//** This keyword controls the rovibrational line list printout. ''LLPRINT=1'' prints the transition moments, ''LLPRINT=2'' the oscillator strengths, ''LLPRINT=3'' the Einstein A coefficients, ''LLPRINT=4'' symmetry information, and ''LLPRINT=5'' vibrational hot bands. Any of these numbers can be combined, e.g. ''LLPRINT=123'' prints the transition moments, the oscillator strengths and the Einstein A coefficients. This keyword or the ''DUMP_IR'' and/or ''DUMP_RAMAN'' keyword have to be set in order to compute rovibrational intensitites. | * **''LLPRINT''=//n//** This keyword controls the rovibrational line list printout. ''LLPRINT=1'' prints the transition moments, ''LLPRINT=2'' symmetry information, ''LLPRINT=3'' the Einstein A coefficients, ''LLPRINT=4'' the oscillator strength, and ''LLPRINT=5'' vibrational hot bands. Any of these numbers can be combined, e.g. ''LLPRINT=123'' prints the transition moments, symmetry information and the Einstein A coefficients. This keyword or the ''DUMP_IR'' and/or ''DUMP_RAMAN'' keyword have to be set in order to compute rovibrational intensitites. |
| * **''NDIMCOR''=//n//** (=2) Order of the $\mu$-tensor expansion within Coriolis coupling terms. ''NDIMCOR=0'' denotes no Coriolis coupling. ''NDIMCOR=1'' considers 0th order terms, ''NDIMCOR=2'' uses 1st order term, ''NDIMCOR=3'' is the highest implemented value and uses 2nd order terms. | * **''NDIMCOR''=//n//** (=2) Order of the $\mu$-tensor expansion within Coriolis coupling terms. ''NDIMCOR=0'' denotes no Coriolis coupling. ''NDIMCOR=1'' considers 0th order terms, ''NDIMCOR=2'' uses 1st order term, ''NDIMCOR=3'' is the highest implemented value and uses 2nd order terms. |
| * **''NDIMDIP''=//n//** (Default is identical to previous VCI calculation) Order of the $n$-mode expansion of the dipole surfaces used for the calculation of the vibrational transition moments in rovibrational intensities. | * **''NDIMDIP''=//n//** (Default is identical to preceding VCI calculation) Order of the $n$-mode expansion of the dipole surfaces used for the calculation of the vibrational transition moments in rovibrational intensities. |
| * **''NDIMPOL''=//n//** (Default is identical to previous VCI calculation) Order of the $n$-mode expansion of the polarizability surfaces used for the calculation of the vibrational transition moments in rovibrational intensities. | * **''NDIMPOL''=//n//** (Default is identical to preceding VCI calculation) Order of the $n$-mode expansion of the polarizability surfaces used for the calculation of the vibrational transition moments in rovibrational intensities. |
| | * **''NDIMQUAD''=//n//** (Default is identical to preceding VCI calculation) Order of the $n$-mode expansion of the quadrupole surfaces used for the calculation of the vibrational transition moments in rovibrational intensities. |
| * **''NDIMROT''=//n//** (=3) Order of the $\mu$-tensor expansion within rotational terms. ''NDIMROT=1'' considers 0th order terms, ''NDIMROT=2'' uses 1st order terms up to ''NDIMROT=4'' for 3rd order terms. | * **''NDIMROT''=//n//** (=3) Order of the $\mu$-tensor expansion within rotational terms. ''NDIMROT=1'' considers 0th order terms, ''NDIMROT=2'' uses 1st order terms up to ''NDIMROT=4'' for 3rd order terms. |
| | * **''NSSW''=//'i-j-k...'//** The nuclear spin statistical weights will be determined automatically. However, the can also be provided explicitly by this keyword. The number of NSSWs must match the number of irreps and the different NSSWs need to be separated by minus signs. |
| * **''PARTF''=//0,1,2//** (= 1 Default) Mode rovibrational partition function. If equals ''0'', then partition function gets not calculated. For ''PARTF=1'' partition function is calculated with separation approximation and for ''PARTF=2'' only all RVCI energies are used. | * **''PARTF''=//0,1,2//** (= 1 Default) Mode rovibrational partition function. If equals ''0'', then partition function gets not calculated. For ''PARTF=1'' partition function is calculated with separation approximation and for ''PARTF=2'' only all RVCI energies are used. |
| * **''PARTF_R_THR''=//value//** (=$10^{-4}$ Default) Threshold for the relative deviation within the iterative determination of the rotational partition function. | |
| * **''PARTF_V_THR''=//value//** (=$10^{-4}$ Default) Threshold for the relative deviation within the iterative determination of the vibrational partition function. | |
| * **''PFIT''=//value//** (=0 Default) Fitting of spectroscopic parameters for asymmetric tops using Watson's reduced operator. ''PFIT=1'' activates the fitting procedure if ''JMAX>0''. IR Intensities are not needed for the fitting! By setting ''PFIT=2'' additional printout of the optimization algorithm is provided. | * **''PFIT''=//value//** (=0 Default) Fitting of spectroscopic parameters for asymmetric tops using Watson's reduced operator. ''PFIT=1'' activates the fitting procedure if ''JMAX>0''. IR Intensities are not needed for the fitting! By setting ''PFIT=2'' additional printout of the optimization algorithm is provided. |
| * **''PFITCUT''=//0,1//** (=0 Default) By default, the whole reference data set is used by PFIT. Setting this keyword to (1) will activate a filter that cuts data points with a high residuum from the data set and improves overall convergence slightly. | * **''PFITCUT''=//0,1//** (=0 Default) By default, the whole reference data set is used by PFIT. Setting this keyword to (1) will activate a filter that cuts data points with a high residuum from the data set and improves overall convergence slightly. |
| * ''RBAS=4'' uses a molecule specific rotational basis (MSRB) generated from a linear combination of Wang combinations. | * ''RBAS=4'' uses a molecule specific rotational basis (MSRB) generated from a linear combination of Wang combinations. |
| * ''RBAS=5'' symmetrized Wang combinations are used, i.e. $|J K \tau> = i^\tau(-1)^\sigma/\sqrt{2} (|JK> + (-1)^{J+K+\tau}|J-K>)$, which results in a real-valued RVCI matrix, while all other bases lead to a complex RVCI matrix. | * ''RBAS=5'' symmetrized Wang combinations are used, i.e. $|J K \tau> = i^\tau(-1)^\sigma/\sqrt{2} (|JK> + (-1)^{J+K+\tau}|J-K>)$, which results in a real-valued RVCI matrix, while all other bases lead to a complex RVCI matrix. |
| * **''RVINTTHR''=//value//** (=10$^{-6}$ Default) Threshold for printing rovibrational lines relative to the intensity of the strongest line. | |
| * **''RAMAN_POLANG''=//value//** (=90 Default) Raman polarization angle defining the prefactors mixing the isotropic and anisotropic Raman transition moments for the calculation of Raman intensities. | * **''RAMAN_POLANG''=//value//** (=90 Default) Raman polarization angle defining the prefactors mixing the isotropic and anisotropic Raman transition moments for the calculation of Raman intensities. |
| * **''RAMAN_FAC(n)''=//value//** Set the prefactors for the isotropic and anisotropic Raman transition moments for the calculation of Raman intensities manually. $n=0$ will set the value for $R_0$, $n=2$ the one for $R_2$. | * **''RAMAN_FAC(n)''=//value//** Set the prefactors for the isotropic and anisotropic Raman transition moments for the calculation of Raman intensities manually. $n=0$ will set the value for $R_0$, $n=2$ the one for $R_2$. |
| * **''RAMAN_LFREQ''=//value//** (=680 Default, in nm) Raman exciting radiation (laser) frequency. | * **''RAMAN_LFREQ''=//value//** (=680 Default, in nm) Raman exciting radiation (laser) frequency. |
| * **''SPARSITY''=//0,1//** (=1 (on) Default) allows to use sparsity within the storage of the RVCI eigenvectors, which also accelerates the calculation of the infrared intensities. | * **''SPARSITY''=//0,1//** (=1 (on) Default) allows to use sparsity within the storage of the RVCI eigenvectors, which also accelerates the calculation of the infrared intensities. |
| * **''SPARSTHR''=//n//** (=5 Default) general sparsity threshold for RVCI eigenvectors. $n$ refers to the actual threshold of $10^{-n}/(J+1)$ with $J$ being the rotational quantum number. | |
| * **''SYM''=//0,1//** (=1 (on) Default) Abelian point group symmetry is exploited within the construction of the RVCI matrix. | * **''SYM''=//0,1//** (=1 (on) Default) Abelian point group symmetry is exploited within the construction of the RVCI matrix. |
| * **''TEMP''=//value//** (=300 Default, in Kelvin) Spectra for different temperatures can be calculated during plotting using the temperature dependent thermal occupation prefactor and the corresponding partition function value. But a maximum temperature is needed for the calculation to define the highest occupied states. This temperature is set by this parameter. | * **''TEMP''=//value//** (=300 Default, in Kelvin) Spectra for a given temperature can be calculated using the temperature dependent thermal occupation prefactor and the corresponding partition function value. |
| * **''THRHOTB''=//n//** (=5d-2 Default) Minimum of the relative thermal occupation for the lower vibrational mode, in order to be considered as a hot band. | * **''THRHOTB''=//n//** (=5d-2 Default) Minimum of the relative thermal occupation for the lower vibrational mode, in order to be considered as a hot band. |
| | * **''THRROTPF''=//value//** (=$10^{-4}$ Default) Threshold for the relative deviation within the iterative determination of the rotational partition function. |
| | * **''THRRVINT''=//value//** (=10$^{-6}$ Default) Threshold for printing rovibrational lines relative to the intensity of the strongest line. |
| | * **''THRSPARS''=//n//** (=5 Default) general sparsity threshold for RVCI eigenvectors. $n$ refers to the actual threshold of $10^{-n}/(J+1)$ with $J$ being the rotational quantum number. |
| | * **''THRVIBPF''=//value//** (=$10^{-4}$ Default) Threshold for the relative deviation within the iterative determination of the vibrational partition function. |
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| ==== Explicit definition of the correlation space ==== | ==== Explicit definition of the correlation space ==== |