CALCULATION OF ANHARMONICITIES IN OVERTONE MODES AND SMALL-CLUSTER SHIFTS OF SPHERICAL-TOP MOLECULES

J. D. FUHR; J. FIOL; E. CORTIZO; P. FAINSTEIN; D. FREGENAL; T. GUOZDEN; E. KAUL; P. KNOBLAUCH; A. LAMAGNA; G. ROZAS; M. ZARCO

Champaign-Urbana

Simposio; International Symposium on Molecular Spectroscopy; 2014

Harmonic and anharmonic vibrational self-consistent field (VSCF) calculations were employed to investigate the fundamental and overtone modes of SF6 molecules. Determination of the Potential Energy Surface (PES) on a multidimensional grid of more than 65000 nodes was performed, and a system of 1D coupled-equations was solved. Corrections to the harmonic approximation for the frequencies of the fundamental modes and their overtones were obtained. Ab-initio calculations to the interaction potential between two molecules as a function of their position and orientation, and the corresponding energies for dimer formation, have been computed. Finally, the effect of dimerization on the molecular frequencies is investigated.