POTENTIAL ENERGY AND DIPOLE MOMENT CURVES FOR THE $^{1,3}\Sigma^{+},\; ^{1,3}\Pi$ ELECTRONIC STATES OF CaO
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Date
1978
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Ohio State University
Abstract
Multiconfiguration self-consistent-field (MCSCF) theory is used to define orbital spaces for the lowest $^{1}\Sigma^{+},\;^{3}\Sigma^{+}$ and $^{3}\Pi$ states of CaO. First-order type configuration interaction calculations are carried out in these optimized orbital spaces to locate the two lowest energy $^{1}\Sigma^{+}$ states, the lowest $^{3}\Sigma^{+}$ state and the lowest $^{1,3}\Pi$ states. The $^{1}\Sigma^{+}$ state is found to be the ground state and lies about 0.4 eV below the $^{1,3}\Pi$ states. The reason appears to be the presence of the charge transfer configuration $C_{a}^{++}O^{--}$ in the $^{1}\Sigma^{+}$ state. Dipole moments for the $^{3}\Sigma^{+}$ and the $^{1,3}\Pi$ states are found to be almost linear functions of the internuclear distance, whereas the dipole moments of the $^{1}\Sigma^{+}$ states are rapidly varying functions of the internuclear distance with values as large as 12 Debyes, Thin will be discussed in terms of a natural orbital population analysis.
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This research has been supported by the U.S. Department of Energy.
Author Institution: Chemistry Division, Argonne National Laboratory
Author Institution: Chemistry Division, Argonne National Laboratory