A theoretical study of the excited states of CrH: Potential energies, transition moments, and lifetimes
(2004) In Journal of Chemical Physics 121(17). p.8194-8200- Abstract
- Ab initio calculations of low-lying electronic states of CrH are presented, including potential energies, dipole and transition dipole moment (TDM) functions, and radiative lifetimes for X (6)Sigma(+), A (6)Sigma(+), 3 (6)Sigma(+), 1 (6)Pi, 2 (6)Pi, 3 (6)Pi, and (6)Delta. Calculation of dynamic correlation effects was performed using the multistate complete active space second-order perturbation method, based on state-averaged complete active space self-consistent-field reference wave functions obtained with seven active electrons in an active space of 16 molecular orbitals. A relativistic atomic natural orbital-type basis set from the MOLCAS library was used for Cr. Good agreement is found between the current calculations and experiment... (More)
- Ab initio calculations of low-lying electronic states of CrH are presented, including potential energies, dipole and transition dipole moment (TDM) functions, and radiative lifetimes for X (6)Sigma(+), A (6)Sigma(+), 3 (6)Sigma(+), 1 (6)Pi, 2 (6)Pi, 3 (6)Pi, and (6)Delta. Calculation of dynamic correlation effects was performed using the multistate complete active space second-order perturbation method, based on state-averaged complete active space self-consistent-field reference wave functions obtained with seven active electrons in an active space of 16 molecular orbitals. A relativistic atomic natural orbital-type basis set from the MOLCAS library was used for Cr. Good agreement is found between the current calculations and experiment for the lowest two (6)Sigma(+) states, the only states for which spectroscopic data are available. Potential curves for the 3 (6)Sigma(+) and 2 (6)Pi states are complicated by avoided crossings with higher states of the same symmetry, thus resulting in double-well structures for these two states. The measured bandhead T-0=27 181 cm(-1), previously assigned to a (6)Pi<--X (6)Sigma(+) transition, is close to our value of T-0=28 434 cm(-1) for the 2 (6)Pi state. We tentatively assign the ultraviolet band found experimentally at 30 386 cm-1 to the 3 (6)Pi<--X (6)Sigma(+) transition for which the computed value is 29 660 cm-1. The A (6)Sigma(+)<--X (6)Sigma(+) TDM and A (6)Sigma(+) lifetimes are found to be in reasonable agreement with previous calculations. (C) 2004 American Institute of Physics. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/139564
- author
- Ghigo, Giovanni LU ; Roos, Björn LU ; Stancil, P C and Weck, P F
- organization
- publishing date
- 2004
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Chemical Physics
- volume
- 121
- issue
- 17
- pages
- 8194 - 8200
- publisher
- American Institute of Physics (AIP)
- external identifiers
-
- wos:000224755700005
- scopus:9744223598
- ISSN
- 0021-9606
- DOI
- 10.1063/1.1794631
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- dc054f1c-c9d5-4e15-b48c-9b9f1b631a13 (old id 139564)
- date added to LUP
- 2016-04-01 12:12:12
- date last changed
- 2023-01-03 05:17:21
@article{dc054f1c-c9d5-4e15-b48c-9b9f1b631a13, abstract = {{Ab initio calculations of low-lying electronic states of CrH are presented, including potential energies, dipole and transition dipole moment (TDM) functions, and radiative lifetimes for X (6)Sigma(+), A (6)Sigma(+), 3 (6)Sigma(+), 1 (6)Pi, 2 (6)Pi, 3 (6)Pi, and (6)Delta. Calculation of dynamic correlation effects was performed using the multistate complete active space second-order perturbation method, based on state-averaged complete active space self-consistent-field reference wave functions obtained with seven active electrons in an active space of 16 molecular orbitals. A relativistic atomic natural orbital-type basis set from the MOLCAS library was used for Cr. Good agreement is found between the current calculations and experiment for the lowest two (6)Sigma(+) states, the only states for which spectroscopic data are available. Potential curves for the 3 (6)Sigma(+) and 2 (6)Pi states are complicated by avoided crossings with higher states of the same symmetry, thus resulting in double-well structures for these two states. The measured bandhead T-0=27 181 cm(-1), previously assigned to a (6)Pi<--X (6)Sigma(+) transition, is close to our value of T-0=28 434 cm(-1) for the 2 (6)Pi state. We tentatively assign the ultraviolet band found experimentally at 30 386 cm-1 to the 3 (6)Pi<--X (6)Sigma(+) transition for which the computed value is 29 660 cm-1. The A (6)Sigma(+)<--X (6)Sigma(+) TDM and A (6)Sigma(+) lifetimes are found to be in reasonable agreement with previous calculations. (C) 2004 American Institute of Physics.}}, author = {{Ghigo, Giovanni and Roos, Björn and Stancil, P C and Weck, P F}}, issn = {{0021-9606}}, language = {{eng}}, number = {{17}}, pages = {{8194--8200}}, publisher = {{American Institute of Physics (AIP)}}, series = {{Journal of Chemical Physics}}, title = {{A theoretical study of the excited states of CrH: Potential energies, transition moments, and lifetimes}}, url = {{http://dx.doi.org/10.1063/1.1794631}}, doi = {{10.1063/1.1794631}}, volume = {{121}}, year = {{2004}}, }