Vibrational relaxation of CH3F in inert gas matrices

Abstract

The deactivation mechanism of the CH stretching fundamentals and bending overtones in matrix isolated CH3F has been determined for dilute samples as a function of host and temperature using infrared laser excited vibrational fluorescence. The decay mechanism is the same for all hosts; depopulation of any of the levels near 3000 cm−1 occurs via rapid (<5 ns) V→V transfer to the CF stretching overtone level 2 ν3. Subsequent stepwise relaxation occurs from 2ν3 to ν3 and from ν3 to ground. Decay rates of 2ν3 and ν3 have been determined through temporal resolution of 1050 and 2100 cm−1 fluorescence, respectively. These rates show a dramatic dependence on host lattice, an increase of two orders of magnitude in going from Xe to Ar matrices. Lifetimes depend only weakly on temperature.