Vibrational relaxation of HOD by collisions with Ar atoms

Abstract

Vibrational relaxation of HOD(v12, v3) molecules by collisions with Ar was studied at 298 K (v12 denotes coupled bending, v2, and OD stretching, v1, vibrational modes and v3 denotes OH stretching mode). The vibrationally excited HOD molecules were generated by exothermic abstraction reactions of OD radicals with 13 different RH reactants and observed by infrared emission from a fast-flow reactor as a function of Ar pressure and reaction time. State-specific relaxation rate constants were obtained by comparison of the time evolution of the experimental vibrational distributions with numerical kinetic calculations for vibrational populations. The relaxation mechanism was based on the relaxation scheme of H2O studied earlier with the addition of specific channels for HOD(v12, v3). Unlike H2O, energy in stretching and bending vibrations of HOD cannot be separated due to close ν1 and 2ν2 energies, which leads to fast collisional equilibration between these Fermi-resonant levels. For relaxation of the only pure bending state (10), a rate constant of (1.5 ± 0.3) × 10−13 cm3 molecule−1 s−1 was obtained. The relaxation rate of higher v12 states linearly increases with quantum number and very likely includes transfer of population from OD stretch levels, v1, to a lower energy bend level. The average rate constants for the loss of population from (01), (02), and (03) stretching states are (1.1 ± 0.3) × 10−14, (3.2 ± 1.0) × 10−14, and (5.6 ± 1.2) × 10−14 cm3 molecule−1 s−1, respectively.