Harmonic oscillator basis functions and Gaussian model potentials for the analysis of anharmonic vibrations*

Abstract

AbstractPotential energy surfaces are mapped onto expansions in Gaussian basis functions in order to examine vibrational anharmonicity in molecules; the Gaussian expansions are constructed to take many‐body effects into account. Subsequent quantum mechanical analyses using harmonic oscillator basis sets are carried out. The appropriate matrix elements needed for the analyses follow using Talmi transformations and several standard integrals involving harmonic oscillator basis functions. Local anharmonicity can be explored with relatively modest expansions of the potential energy surfaces. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001