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

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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.

Detaljer

Författare
  • Giovanni Ghigo
  • Björn Roos
  • P C Stancil
  • P F Weck
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Forskningsområden

Ämnesklassifikation (UKÄ) – OBLIGATORISK

  • Teoretisk kemi
Originalspråkengelska
Sidor (från-till)8194-8200
TidskriftJournal of Chemical Physics
Volym121
Utgivningsnummer17
StatusPublished - 2004
PublikationskategoriForskning
Peer review utfördJa