Anharmonic Vibrational Motions In C60: A Potential Energy Surface Derived From Vibrational Self-Consistent Field Calculations

Abstract

A potential energy surface (PES) is developed for C60 designed to describe vibrational motions valid in the anharmonic limit. The PES is based on a previously existing one that is fit to the harmonic fundamentals and is then modified to generate anharmonicity of all orders and in all terms, but without additional fitted parameters. The resulting Cartesian vibrational motions are decomposed into normal modes, and the anharmonic expansion coefficients are calculated including 2-mode couplings and up to 4th order. The resulting PES is used in a vibrational self-consistent field (VSCF) algorithm to calculate the anharmonically corrected fundamental frequencies. The parameters are then fit to fundamental infrared and Raman frequencies. While it is not possible to assign combination and overtone transitions with sufficient experimental accuracy, conclusions about the effects of anharmonic vibrational coupling in C60 are described.