Vibrational relaxation of matrix-isolated CH/sub 3/F and HCl

Kinetic and spectroscopic studies have been performed on CH/sub 3/F and HCl as a function of host matrix and temperature. Temporally and spectrally resolved infrared fluorescence was used to monitor the populations of both the initially excited state and the lower lying levels which participate in the relaxation process. For CH/sub 3/F, relaxation from any of the levels near 3.5 ..mu.., i.e. the CH stretching fundamentals or bend overtones, occurs via rapid (< 5 ns) V ..-->.. V transfer to 2..nu../sub 3/ with subsequent relaxation of the ..nu../sub 3/ (CF stretch) manifold. Lifetimes of 2..nu../sub 3/ and ..nu../sub 3/ were determined through overtone, ..delta..V = 2, and fundamental fluorescence. These lifetimes show a dramatic dependence on host lattice, an increase of two orders of magnitude in going from Xe and Ar matrices. Lifetimes depend only weakly on temperature. The relaxation of 2..nu../sub 3/ and ..nu../sub 3/ is consistent with a model in which production of a highly rotationally excited guest via collisions with the repulsive wall of the host is the rate limiting step. For HCl, lifetimes of v = 1,2,3 have been determined. In all hosts, the relaxation is non-radiative. For a given vibrational state, v, the relaxation rate increases in the series k(Ar) < k(Kr) < k(Xe). The dependence of the relaxation rate; on v is superlinear in all matrices, the deviation from linearity increasng in the order Ar < Kr < Xe. The relaxation rates become more strongly temperature dependent with increasing vibrational excitation. The results are consistent with a mechanism in which complex formation introduces the anisotropy necessary to induce a near resonant V ..-->.. R transition in the rate limiting step