Semiempirical calculation of the absolute solvation shift of electronic and vibrational spectra of molecules in the gas-solution phase transition

Abstract

Calculations of the main components of the absolute solvation shift of Δυ∑a, f, R optical absorption, emission, and Raman spectra of molecules in the gas-solution phase transition for solutions of several diatomic (HCl, DCl, H2, D2) and polyatomic (anthracene, 3-and 4-aminophthalimide) substances in some polar and nonpolar solvents are presented. The calculations are made by a new method of the semiempirical theory, which was proposed by the author earlier and makes such calculations possible for the first time. It is shown that the given theory adequately describes the photophysical effect under study and provides a correct prediction of the values of Δυ∑a, f, R, which differ for different systems by more than three orders of magnitude (from several inverse centimeters for vibrational spectra of H2 and D2 to many thousands of inverse centimeters for electronic fluorescence spectra of solutions of aminosubstituted derivatives of phthalimide).