Solvent Field Corrections for Electric Dipole and Rotatory Strengths

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Abstract
Quantum‐mechanical perturbation theory is applied to the evaluation of the electric dipole strength and the rotatory strength of a condensed system of negligibly overlapped, randomly oriented solute and solvent molecules. 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 heretofore considered is achieved. In particular, 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. The complexity of terms and level of approximation cannot be expected to yield more than semiquantitative relationships, but the important solvent and solute variables are identified.