Vibrational overtone spectra of N–H stretches and intramolecular dynamics on the ground and electronically excited states of methylamine

Abstract

The vibrational pattern and energy flow in the N-H stretch manifolds and the dissociation dynamics of methylamine (CH(3)NH(2)) were investigated via vibrationally mediated photodissociation. Action spectra and Doppler profiles, reflecting the yield of the ensuing H photofragments, versus near infrared/visible vibrational excitation and UV excitation, respectively, were measured. The jet-cooled action spectra and the simultaneously measured room temperature photoacoustic spectra of the first to third N-H stretching overtones exhibit broad features, somewhat narrower in the former, consisting of barely recognized multiple bands. Two phases of fitting of the spectroscopic data were performed. In the first phase, the raw data were analyzed to obtain band positions, types, intensities, and transition linewidths. In the second, the information derived from the first phase was then used as data in a fit to joint local mode/normal mode (LM/NM) and NM Hamiltonian parameters. The derived parameters predicted well band positions and allowed band assignment. The LM/NM Hamiltonian and the extracted Lorentzian linewidths enabled the determination of the initial pathways for energy redistribution and the overall temporal behavior of the N-H stretch and doorway states, as a result of Fermi couplings and interactions with bath states. The results indicate a nonstatistical energy flow in the V=2 manifold region, pointing to the dependence of the coupling on specific low order resonances rather than on the total density of bath states. The Doppler profiles suggest lower average translational energies for the released H photofragments, in particular, for V=3 and 4 as compared to V=1 and 2, implying a change in the mechanism for bond cleavage.