THE ELECTRONIC STRUCTURE OF $B_{2}$

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1977

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Ohio State University

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Extended ab initio configuration interaction calculations of the potential curves of the 3Σg,5Σu, and 3Σu states of B2, have established that the ground state is of 3Σg symmetry. The Douglas-Herzberg emission system1 near 3200 \AA results from transitions between the second root of the 3Σu symmetry and the ground 3Σg state. The lowest 5Σu state, suggested by previous theoretical studies,2,3 as the ground state, is found to lie approximately 1000 cml above the 3Σg state. The close agreement between calculated and experimental spectroscopic data identifies the states responsible for the Douglas-Herzberg transition. The calculated results, with the experimental values in parentheses, are:\begin{eqnarray*} T_{e} &=& 31438 cm^{-1} (30546.1)\ R_{e}(^{3}\Sigma_{g}^{-}) &=& 1.622 \AA (1.590)\ \omega_{e}(^{3}\Sigma_{g}^{-}) &=& 988.5 cm^{-1} (1035.2)\ R_{e}(^{3}\Sigma_{u}^{-}) &=& 1.660 \AA (1.625)\ \omega_{e}(^{3}\Sigma_{u}^{-}) &=& 884.5 cm^{-1} (929.3)\ \end{eqnarray*}

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1A. E. Douglas and G. Herzberg, Can. J. Res. A18, 165 (1940). 2A. A. Padgett and V. Griffing, J. Chem. Phys. 30, 1286 (1959). 3C. F. Bender and E. R. Davidson, J. Chem. Phys. 46, 3313 (1967).


Author Institution: IBM Research Laboratories

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