Variational method for calculating the anharmonic vibrations of polyatomic molecules using a combined morse-anharmonic basis taking into account the fragmentary structure of molecules

Abstract

A method of variational solution of anharmonic vibration problems using a mixed Morse—anharmonic basis is proposed. The basis functions are the products of the Morse oscillator eigenfunctions for vibrations of peripheral bonds, the harmonic oscillator eigenfunctions for almost harmonic skeletal and deformation vibrations, and the anharmonic basis functions for essentially anharmonic skeletal and deformation vibrations. The anharmonic basis wave functions are taken as a linear combination of the Morse and harmonic oscillator eigenfunctions. The introduction of the combined Morse—anharmonic functions allows one to factorize the solution of a problem into a series of individual blocks according to the fragmentary structure of molecules.