Vibrational relaxation of HCN(001) by the noble gases, O2, N2 and CO

Abstract
The tuned output from an optical parameteric oscillator has been used to excite HCN to its (0001) level for measurements of vibrational energy transfer. By observing time-resolved infrared fluorescence from the (0001) level in the presence of different collision partners, the following rate constants (k/cm3 molecule–1 s–1) were obtained at 297 ± 4 K: kHe=(6.4 ± 0.4)×10–15; kNe=(6.3 ± 0.6)×10–15; kAr=(6.5 ± 0.5)×10–15; kKr=(7.1 ± 0.7)×10–15; kO2 =(1.34 ± 0.05)×10–14; kN2 =(2.2 ± 0.2)×10–14; kCO=(3.3 ± 0.2)×10–14. It is argued that, in all cases, relaxation from the (0001) level is rate-determining and that the dominant process is probably transfer into neighbouring levels, such as (1200), associated with the ν1 and ν2 modes.

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