Nonspecific Solvation and Vibrational Spectra of Cryosolutions. A Semiempirical Theory of the Effect of the Solvent on the Positions of Vibrational Bands of Diatomic Molecules

摘要

On the basis of the new results obtained in recent years and related to a further development of continual approach (approximation) in the spectroscopy of intermolecular interactions, a consistent semiempirical theory of the influence of nonspecific solvation on the positions of vibrational bands of diatomic molecules is suggested for the first time. The refined relationships making it possible to calculate the principal spectral-shift components defined by universal intermolecular repulsive forces and by attractive forces of dispersion, induction, and induction-resonance origin were derived. It is shown by an example of IR absorption spectra of HCl and DCl solutions in various nonpolar solvents (liquefied N_2, Ar, Kr, and Xe; and CCl_4) that the absolute spectral-shift values obtained in the context of modern semiempirical solvation theory based on the concept of the Onsager reactive field are in a good qualitative agreement with experimental data.