INTRAMOLECULAR ENERGY-TRANSFER IN HIGHLY VIBRATIONALLY EXCITED METHANOL .1. ULTRAFAST DYNAMICS

Vibrational overtone excitation of jet-cooled methanol, in combination with infrared laser assisted photofragment spectroscopy (IRLAPS) dete ction, reveals OH stretch bands that are significantly simplified with respect to room-temperature spectra. The simplification afforded by j et-cooling permits the observation of spectral splitting on the order of 50 cm(-1) in the region of the 5 nu(1) OH stretch overtone band. Tr acking 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, 4 nu(1) + nu(2). Careful examination of the spectra reveals that this strong interacti on arises from a fourth-order anharmonic term in the Hamiltonian that couples the OH and CH ends of the molecule. These frequency domain res ults indicate that subsequent to coherent excitation of the 5 nu(1) ba nd, methanol would undergo energy redistribution to the methyl part of the molecule on a time scale of similar to 130 fs. This work also sug gests that similar strong resonances may occur more generally in molec ules that possess two different high-frequency oscillators in close pr oximity. (C) 1997 American Institute of Physics. [S0021-9606(97)02544- 0].