A theoretical study of the excited states of CrH: Potential energies, transition moments, and lifetimes
(2004) In Journal of Chemical Physics 121(17). p.81948200 Abstract
 Ab initio calculations of lowlying 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 secondorder perturbation method, based on stateaveraged complete active space selfconsistentfield reference wave functions obtained with seven active electrons in an active space of 16 molecular orbitals. A relativistic atomic natural orbitaltype 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 lowlying 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 secondorder perturbation method, based on stateaveraged complete active space selfconsistentfield reference wave functions obtained with seven active electrons in an active space of 16 molecular orbitals. A relativistic atomic natural orbitaltype 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 doublewell structures for these two states. The measured bandhead T0=27 181 cm(1), previously assigned to a (6)Pi<X (6)Sigma(+) transition, is close to our value of T0=28 434 cm(1) for the 2 (6)Pi state. We tentatively assign the ultraviolet band found experimentally at 30 386 cm1 to the 3 (6)Pi<X (6)Sigma(+) transition for which the computed value is 29 660 cm1. 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:
http://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
 external identifiers

 wos:000224755700005
 scopus:9744223598
 ISSN
 00219606
 DOI
 10.1063/1.1794631
 language
 English
 LU publication?
 yes
 id
 dc054f1cc9d54e15b48c9b9f1b631a13 (old id 139564)
 date added to LUP
 20070717 10:00:06
 date last changed
 20190220 04:21:03
@article{dc054f1cc9d54e15b48c9b9f1b631a13, abstract = {Ab initio calculations of lowlying 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 secondorder perturbation method, based on stateaveraged complete active space selfconsistentfield reference wave functions obtained with seven active electrons in an active space of 16 molecular orbitals. A relativistic atomic natural orbitaltype 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 doublewell structures for these two states. The measured bandhead T0=27 181 cm(1), previously assigned to a (6)Pi<X (6)Sigma(+) transition, is close to our value of T0=28 434 cm(1) for the 2 (6)Pi state. We tentatively assign the ultraviolet band found experimentally at 30 386 cm1 to the 3 (6)Pi<X (6)Sigma(+) transition for which the computed value is 29 660 cm1. 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 = {00219606}, language = {eng}, number = {17}, pages = {81948200}, 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}, }