CENTRIFUGAL DISTORTIONS IN MOLECULES: AN AB INITIO APPROACH
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Date
1986
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Ohio State University
Abstract
An ab initio approach to the theoretical description of centrifugal distortions in molecules is $presented.^{1}$ The method is based on the calculation of the electronic energy changes and gradients accompanying rotationally induced distortions. A centrifugal distortion pathway in nuclear coordinate space is defined. Results are presented at the $HF/6-31G^{\ast\ast}$ level for $NH_{3}, CH_{4}, BF_{3}$, and $SF_{6}$, and at the Gullemin-Zener level for $H_{2}^{+}$. Quartic centrifugal distortion parameters are computed for each molecule, with distortion anisotropies presented in the form of tensor coefficients. Centrifugally induced electric dipole moment coefficients are presented for $CH_{4}$ and $BF_{3}$ together with dipole moment changes for $NH_{3}$. Agreement with experiment and with conventional theoretical descriptions is generally quite satisfactory, particularly for the tensor coefficients representing the cubic anisotropy in the distortions of the spherical tops $CH_{4}$ and $SF_{6}$.
Description
$^{1}$ L. L. Lohr and J.-M. J. Popa, J. Chem. Phys., in press. Address of Lohr and Popa: Department of Chemistry, University of Michigan, Ann Arbor, Michigan, 48109.
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