Vibrational Relaxation of the 2ν5 Overtone of CDCl3 Following Tea CO2 Laser Excitation of the ν4 Mode
The time variation of the 2ν5 fluorescence intensity was measured in CDCl3 excited in the ν4 C–D bending mode by a TEA CO2 laser operating on the 10P(48) line. A fast rise of the fluorescence, with a time constant ≤ 1 μs Torr, was first observed, showing that a fast equilibration of population occurs between the ν4 and ν5 modes through a ν4 ↔ ν5 Coriolis-assisted intermode transfer and a ν5 ↔ 2ν5 near-resonant ladder-climbing process. Then a first fast fluorescence decay was observed and attributed to a (ν4, ν5) → ν2 intermode transfer with a rate constant of (7.10 ± 1.13)ms-1 Torr-1. At last, a much slower decay, with a rate constant of 0.111 ± 0.015 ms-1 Torr-1, results from the less efficient intermode transfer and V–T,R deexcitation processes involving the ν3 and ν6 states, and which compete to relax the gas to a thermodynamic equilibrium.