A CASSCF/MRCI study of the low-lying Rydberg states of ClO

Citation
Ic. Lane et As. Orr-ewing, A CASSCF/MRCI study of the low-lying Rydberg states of ClO, MOLEC PHYS, 98(12), 2000, pp. 793-806
Citations number
39
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
MOLECULAR PHYSICS
ISSN journal
0026-8976 → ACNP
Volume
98
Issue
12
Year of publication
2000
Pages
793 - 806
Database
ISI
SICI code
0026-8976(20000620)98:12<793:ACSOTL>2.0.ZU;2-W
Abstract
An ab initio calculation has been performed on the lowest seven doublet and six quartet Rydberg states of ClO at the CASSCF/MRCI level and with basis sets suitable for the extended molecular orbitals of such states (aug-cc-pV TZ with up to eleven extra Gaussian functions). Calculations on the quartet states reveal the energy ordering of Rydberg orbitals to be 4s sigma, 4p p i, 4p sigma, 3d delta, 3d sigma and 3d pi. The calculated doublet ab initio potential curves confirm experimental assignments of the C(2)Sigma(-) and F(2)Sigma(-) states but require reassignments for the symmetries of the D ( (2)Delta), E ((II)-I-2) and H ((2)Delta) Rydberg states. These revisions ar e supported by spin-orbit coupling calculations that suggest the separation between the Omega components is small. In addition, a (2)Sigma(+) State ha s been identified as the likely upper state for two previously unassigned v ibronic bands recorded in absorption studies.