SINGLE CENTER CALCULATIONS ON THE EXCITED STATES OF THE EQUILATERAL $H_{a}^{+}$ MOLECULE
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Date
1970
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Publisher
Ohio State University
Abstract
The single-center expansion configuration-interaction $method^{1}$ has been used to examine the low lying electronically excited states of the $H_{3}^{+}$ molecule (equilateral triangular $H_{3}^{+}$ with $D_{th}$ symmetry). The expansion center for the electronic wavefunctions was placed in the plane of the molecule, equidistant from the three hydrogen nuclei. The wavefunction was expanded as a sum of two-electron configurations, each consisting of an antisymmetrized product of symmetry adapted Stater orbitals. The energy of each state was minimized with respect to the non-linear orbital parameters. For each of the electronic states considered, ($^{3}A_{1}^{\prime}, ^{1}A_{2}^{\prime}^{\prime}, ^{3}A_{2}^{\prime}^{\prime}, ^{1}E_{1}^{\prime}, ^{3}E_{1}^{\prime}$) the energy was evaluated at several values of the internuclear separation. Of the above states, only the $^{1}A_{2}^{\prime}^{\prime}$ and the $^{a}A_{2}^{\prime}^{\prime}$ states were found to be bound with respect to the symmetric stretching coordinate. The other states were purely repulsive. Comparisons, where possible, were made with previous $calculations^{2}$, and the single-center method was found to compare favorably with other methods of calculation. The oscillator strengths of the allowed transitions, $^{1}A_{1}^{\prime}\rightarrow ^{1}A_{2}^{\prime}^{\prime}$ and $^{1}A_{1}^{\prime}\rightarrow ^{1}E^{\prime}$, were also calculated.
Description
$^{1}$E. F. Hayes and R. G. Parr, J. Chem. Phys. 47, 3961 (1967), and references therein. $^{2}$H. Conroy, J. Chem. Phys. 51, 3979 (1969), and references therein.""
Author Institution: School of Chemistry, Georgia Institute of Technology
Author Institution: School of Chemistry, Georgia Institute of Technology