A CASSCF/MRCI study of the low-lying Rydberg states of CIO |
| |
Authors: | IAN C. LANE ANDREW J. ORR-EWING |
| |
Affiliation: | School of Chemistry , University of Bristol , Cantock's Close, Bristol, BS8 1TS, UK |
| |
Abstract: | An ab initio calculation has been performed on the lowest seven doublet and six quartet Rydberg states of CIO at the CASSCF/MRCI level and with basis sets suitable for the extended molecular orbitals of such states (aug-cc-pVTZ with up to eleven extra Gaussian functions). Calculations on the quartet states reveal the energy ordering of Rydberg orbitals to be 4sσ, 4pπ, 4pσ;, 3dδ, 3dσ and 3dπ. The calculated doublet ab initio potential curves confirm experimental assignments of the C2Σ- and F2Σ- states but require reassignments for the symmetries of the D (2Δ), E (2Π) and H (2Δ) Rydberg states. These revisions are supported by spin-orbit coupling calculations that suggest the separation between the Ω components is small. In addition, a 2Σ+ state has been identified as the likely upper state for two previously unassigned vibronic bands recorded in absorption studies. |
| |
Keywords: | |
|
|