Campus Units

Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

10-2001

Journal or Book Title

Journal of Chemical Physics

Volume

115

Issue

16

First Page

7393

Last Page

7400

DOI

10.1063/1.1402170

Abstract

The spin-orbit coupling constants (Av+) for O+2(A 2Πu,v+=0–17) and O+2(a 4Πu,v+=0–25) were computed based on the Pauli–Breit Hamiltonian with one and two electron terms for comparison with experimental measurements. In the present theoretical study, the vibrational wave functions are obtained using the potential energy curve calculated at the multireference configuration interaction (MRCI) level of theory, with single and double excitations from the complete active space self-consistent field (CASSCF) reference wave function. The electronic wave functions and spin-orbit coupling constants are obtained at the CASSCF and restricted MRCI levels. The effect on Av+ for O+2(A 2Πu,v+) and O+2(a 4Πu,v+) due to interactions of the O+2(A 2Πu,v+), O+2(a 4Πu,v+), and O+2(2Σ+u)states is examined. The theoretical Av+ predictions for O+2(A 2Πu,v+) are found to be consistent with the experimental finding that O+2(A 2Πu) is an inverted spin-orbit state at low v+ levels and becomes a regular spin-orbit state at higher v+ levels. Good accord between theoretical predictions and experimental results for O+2(A 2Πu,v+=0–12) is observed with discrepancies in the range of 2–10 cm−1. In the case of O+2(a 4Πu,v+), excellent agreement between theoretical ab initio and experimental results is found with a discrepancy of 2–5 cm−1. Our effort to theoretically reproduce experimental fine structure in the Av+ curve for O+2(a 4Πu,v+) based on interstate vibrational interactions has met with limited success.

Comments

The following article appeared in Journal of Chemical Physics 115 (2001): 7393, and may be found at doi:10.1063/1.1402170.

Rights

Copyright 2001 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.

Copyright Owner

American Institute of Physics

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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