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| vibration_correlation_programs [2024/08/29 09:24] – rauhut | vibration_correlation_programs [2024/11/13 10:18] (current) – rauhut |
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| T. Mathea, G. Rauhut, //Advances in vibrational configuration interaction theory - part 1: Efficient calculation of vibrational angular momentum terms.// [[https://onlinelibrary.wiley.com/doi/abs/10.1002/jcc.26762|J. Comput. Chem.]] **42**, 2321–2333 (2021).\\ | T. Mathea, G. Rauhut, //Advances in vibrational configuration interaction theory - part 1: Efficient calculation of vibrational angular momentum terms.// [[https://onlinelibrary.wiley.com/doi/abs/10.1002/jcc.26762|J. Comput. Chem.]] **42**, 2321–2333 (2021).\\ |
| T. Mathea, T. Petrenko, G. Rauhut, //Advances in vibrational configuration interaction theory - part 2: Fast screening of the correlation space.//. [[https://onlinelibrary.wiley.com/doi/abs/10.1002/jcc.26764|J. Comput. Chem.]] **43**, 6–18 (2022).\\ | T. Mathea, T. Petrenko, G. Rauhut, //Advances in vibrational configuration interaction theory - part 2: Fast screening of the correlation space.//. [[https://onlinelibrary.wiley.com/doi/abs/10.1002/jcc.26764|J. Comput. Chem.]] **43**, 6–18 (2022).\\ |
| T. Mathea, G. Rauhut, //Assignment of vibrational states within configuration interaction calculations//, [[https://dx.doi.org/10.1063/5.0009732|J. Chem. Phys.]] **152**, 194112 (2020).\\ | B. Schröder, G. Rauhut, //From the automated calculation of potential energy surfaces to accurate vibrational spectra//, [[https://doi.org/10.1021/acs.jpclett.4c00186|J. Phys. Chem. Lett.]] **15**, 3159 (2024).\\ |
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| * **''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'' 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. |
| * **''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. |
| * **''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 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. |
| * **''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 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. |
| * **''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. |
| * **''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_R_THR''=//value//** (=$10^{-4}$ Default) Threshold for the relative deviation within the iterative determination of the rotational partition function. |
| * ''RBAS=3'' refers to a molecule specific rotational basis (MSRB) obtained from a linear combination of primitive symmetric top functions. | * ''RBAS=3'' refers to a molecule specific rotational basis (MSRB) obtained from a linear combination of primitive symmetric top functions. |
| * ''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, which result 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. |
| * **''RCI''=//n//** (=0 Default) Activates the approximation for RCI calculations to save computational time, but removes any rovib. coupling. Recommended only to get a first overview of the spectrum. RCI=0 performs RVCI calculations. | |
| * **''RVINTTHR''=//value//** (=10$^{-6}$ Default) Threshold for printing rovibrational lines relative to the intensity of the strongest line. | * **''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. |
| * **''SYM''=//0,1//** (=1 Default) Abelian point group symmetry is exploited within the construction of the RVCI matrix. | * **''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. |
| * **''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 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. |
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| * **''SAVE''=//record//** This keyword specifies the record where to dump the VCI information. | * **''SAVE''=//record//** This keyword specifies the record where to dump the VCI information. |
| * **''START''=//record//** This card specifies the record from where to read the VSCF information. As the VSCF information usually is stored in the same record as the polynomials, it is usually defined in the ''POLY'' program. | * **''START''=//record//** This card specifies the record from where to read the VSCF information. As the VSCF information usually is stored in the same record as the polynomials, it is usually defined in the ''POLY'' program. |
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| ===== The vibrational Møller-Plesset programs (VMP2, VMP3, VMP4) ===== | ===== The vibrational Møller-Plesset programs (VMP2, VMP3, VMP4) ===== |
| ''VMPx'',//options// | ''VMPx'',//options// |
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| The ''VMPx'' (x=2,3,4) programs allow to perform 2nd to 4th order vibrational Møller-Plesset calculations. Most of the keywords as described for the ''VCI'' program are also valid for these perturbational programs, i.e. ''%%CITYPE, LEVEX, CIMAX, NGRID, NDIM, NBAS, VAM, DIPOLE, MPG%%'' and ''INFO''. | The ''VMPx'' (x=2,3,4) programs allow to perform 2nd to 4th order vibrational Møller-Plesset calculations. 3rd and 4th order perturbation theory is only available for polynomial based PESs. Any properties (except energies) will always be computed at the level of VMP2. Most of the keywords as described for the ''VCI'' program are also valid for these perturbational programs, i.e. ''%%CITYPE, LEVEX, CIMAX, NDIM, VAM, MPG%%'' and ''INFO''. |
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| | The following //additional options// are available: |
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| | * **''QDEG''=//n//** (=0 default) Quasi-degenerate VMP2 theory (QDVMP2) can be called by ''QDEG=1'' for polynomial based PESs. |
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| <code> | <code> |
| mp2 | mp2 |
| optg | optg |
| {frequencies,symm=auto | frequencies,symm=auto |
| print,low=50} | |
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| label1 | label1 |