Effective harmonic oscillator description of anharmonic molecular vibrations

Abstract

The validity of an effective harmonic oscillator approximation for anharmonic molecular vibrations is tested and compared with vibrational self consistent field and vibrational configurational interaction results. The effective harmonic oscillator is constructed variationally, by taking the trial wave function as a harmonic oscillator eigenfunction with the centroid and width parameter as variational paraeters. It is found that the effective harmonic oscillator approximation provides a description of the anharmonic eigenstates very similar to the vibrational self consistent field results. Coriolis coupling is also included in these studies.