Anharmonic Force Fields and Perturbation Theory in the Interpretation of Vibrational Spectra of Polyatomic Molecules

Abstract

The problem of describing real vibrational spectra of large molecules in terms of perturbation theory is considered. Equations necessary for presenting theoretical anharmonic force fields in various coordinate systems (Cartesian, normal, and internal curvilinear) are discussed. A review of second-order perturbation theory equations necessary for calculating certain spectroscopic values (anharmonicity constants, rotational-vibrational interaction, etc.) is given. A scheme for including resonances based on the construction of the interaction matrix between vibrational transitions of various types is described. This scheme can be used as a basis for anharmonic calculations of vibrations of medium-sized molecules.