THEORETICAL DETERMINATION OF THE LIFETIMES OF THE INDIVIDUAL VIBRATIONAL-ROTATIONAL LEVELS OF THE $A^{2}\Sigma^{+}$ STATE OF OH AND 0D
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Date
1979
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Ohio State University
Abstract
The lifetimes of the Individual vibrational-rotational level of the $A^{2}\Sigma^{+}$ state of OH(OD) have been determined theoretically. Contributions from both radiative and non-radiative (pre-dissociative) processes are considered, Potential energy curves are presented for the $X^{2}\Pi$ and $A_{2}\Sigma^{+}$ bound states and the $^{4}\Sigma^{-}, ^{2}\Sigma^{-}$ and $^{2}\Pi$ repulsive states. These potential curves were generated from self-consistent-field plus configuration-interaction calculations using both a near Hartree-Fock Slater basis and a DZP Cartesian gaussian basis. Results for the electronic transition moment between the X and A states, and the spin-orbit matrix elements between the A state and the repulsive states as a Function of internuclear distance are presented. Computed lifetimes are in good agreement with experiment. It is conclusively shown that the $^{4}\Sigma^{-}$ state accounts for the weak predissociation in the v = 0-2 vibrational levels while the $^{4}\Pi$ state is principally responsible for the much stronger predissotiation in the higher vibrational levels. Comparison of experiment and theory provides a good estimate of the crossing points of the rotation less potentials.
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