CHARGE FLUX AND ATOMIC POLAR TENSORS
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Date
1977
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Publisher
Ohio State University
Abstract
Recent developments in the interpretation of infrared intensities have led to a renewed interest in their determination. Several models have been used and the purpose of this work is to display their interrelation. To avoid the solution of the normal coordinate problem, inherent in the computation of $\partial\mu\sqrt\partial S_{j}^{\prime}$ or polar $tensors,^{1}$ a sum $rule^{2}$ defining average effective charges has been introduced. Another analysis invokes a model in which equilibrium, effective atomic charges and charge fluxes are used as parameters in defining the $\partial\mu\sqrt\partial S_{j}^{\prime}$. The connections between the average effective charges and atomic polar $tensors^{1b}$ and between the average effective charges and the charge flux $model^{2b}$ have been previously demonstrated, and the present work will emphasize the relation between atomic polar tensor elements and the charge flux model. A simple method for the determination of the form of the atomic polar tensors will be explained. It will be shown that the atomic polar tensor elements can be expressed as a combination of equilibrium charges and charge fluxes. The question of transferability of polar tensor elements will be discussed and the atomic anisotropy will be explained, for a few systems, in terms of charge flux.
Description
$^{1}$(a)J. F. Biarge, J. Herranz, and J. Morcillo, Ann. R. Soc. Esp. Fis. Quim. Ser. A57, 81 (1961). (b)W. B. Person and J. H. Newton, J. Chem, Phys. 61, 1040 (1974). $^{2}$(a)W. T. King G. B. Mast, P. P. Blanchett, J. Chem. Phys. 56, 4440 (1972). (b)W. T. King and G. B. Mast, J. Phys. Chem. 80, 2521 (1976). $^{3}$J. C. Decius, J. Mol. Spectrosc. 57, 348 (1975).
Author Institution: Department of Chemistry, Oregon State University
Author Institution: Department of Chemistry, Oregon State University