Intramolecular energy transfer in highly vibrationally excited methanol. I. Ultrafast dynamics

Abstract

Vibrational overtone excitation of jet-cooled methanol, in combination with infrared laser assisted photofragment spectroscopy (IRLAPS) detection, reveals OH stretch bands that are significantly simplified with respect to room-temperature spectra. The simplification afforded by jet-cooling permits the observation of spectral splitting on the order of 50 cm−1 in the region of the 5ν1 OH stretch overtone band. Tracking this splitting as a function of OH stretch vibrational level in combination with isotopic substitution studies allows us to identify the perturbing state as the combination level involving four quanta of OH stretch and one quantum of CH asymmetric stretch, 4ν1+ν2. Careful examination of the spectra reveals that this strong interaction arises from a fourth-order anharmonic term in the Hamiltonian that couples the OH and CH ends of the molecule. These frequency domain results indicate that subsequent to coherent excitation of the 5ν1 band, methanol would undergo energy redistribution to the methyl part of the molecule on a time scale of ∼130 fs. This work also suggests that similar strong resonances may occur more generally in molecules that possess two different high-frequency oscillators in close proximity.