LEVEL SHIFTS IN THE $B^{3}\Sigma^{-}_{u}$ STATE OF MOLECULAR OXYGEN
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Date
1988
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Ohio State University
Abstract
The $B^{3}\Sigma^{-}_{u}$ state of molecular oxygen (the upper state of the Schumann Rung band system) is predissociated by several repulsive continuum states including the $^{1}\Pi_{u}, ^{3}\Pi_{u}, ^{5}\Pi_{u}$ and $2 3^{1}\Sigma_{u}$ states. In an extension of the work of Julienne and $Krauss^{1}$, who first showed that the $^{3}\Pi_{u}$ state is the dominant perturbative state, we have determined an empirical representation for the $^{5}\Pi_{u}$ state which yields a smooth deperturbation in the second vibrational energy differences of the three isotopic molecules $^{16}O_{2}, ^{16}O^{18}O$ and $^{18}O_{2}$. The $^{5}\Pi_{u}$ state is found to cross the $B^{3}\Sigma^{-}_{u}$ state at $1.880 {\AA}$ with a slope at the crossing point of $40000 cm^{-1} {\AA}^{-1}$ and the coupling strength between the $^{5}\Pi_{u}$ and $B^{3}\Sigma^{-}_{u}$ states is $65 cm^{-1}$.
Description
This work is supported by NSF Grant ATM-87-13204 to Harvard University. $^{1}$ P.S. Julienne and M. Kraus, J. Mol. Spectrosc. 56, 270 (1975).
Author Institution: Department of Chemistry, Harvard University; Harvard-Smithsonian Center for Astrophysics, Harvard University
Author Institution: Department of Chemistry, Harvard University; Harvard-Smithsonian Center for Astrophysics, Harvard University