SOLVENT FIELD CORRECTIONS FOR ELECTRIC DIPOLE AND ROTATORY STRENGTHS
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Date
1964
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Publisher
Ohio State University
Abstract
Quantum mechanical perturbation theory is applied to the evaluation of the electric dipole strength and the rotatory strength of a condensed system of randomly-oriented solute and solvent molecule with negligible overlap of wavefunctions. Besides the traditional Lorentz field corrections, a correction factor is obtained which is a function of inductive and dipolar solute-solvent interactions. An extension of the types of intermolecular force fields over those heretofore considered is achieved. The effect of solvent fields due to solvent-molecule static dipole moment is predicted to be a decrease in solute absorption intensity and optical activity. A test of the relationship for electric dipole strength is presented using Brooker-type merocyanine dyes in polar and nonpolar solvents.
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Author Institution: Department of Chemistry, Tulane University