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A theoretical study of the excited states of CrH: Potential energies, transition moments, and lifetimes

Ghigo, Giovanni LU ; Roos, Björn LU ; Stancil, P C and Weck, P F (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)
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author
organization
publishing date
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
external identifiers
  • wos:000224755700005
  • scopus:9744223598
ISSN
0021-9606
DOI
10.1063/1.1794631
language
English
LU publication?
yes
id
dc054f1c-c9d5-4e15-b48c-9b9f1b631a13 (old id 139564)
date added to LUP
2007-07-17 10:00:06
date last changed
2017-07-30 03:45:08
@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&lt;--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&lt;--X (6)Sigma(+) transition for which the computed value is 29 660 cm-1. The A (6)Sigma(+)&lt;--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},
  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},
  volume       = {121},
  year         = {2004},
}