Energy transfer in the 31,214151 Fermi-resonant states of acetylene. I. Rotational energy transfer

Frost, Michael J.
June 1993
Journal of Chemical Physics;6/1/1993, Vol. 98 Issue 11, p8572
Academic Journal
An infrared–ultraviolet double resonance technique is used to probe the state-to-state rotational energy transfer dynamics of self-relaxation in acetylene. The output of an optical parametric oscillator at ∼3 μm is used to excite C2H2 to a rotational level within one of its Fermi-resonant 31,214151 states. By fixing this wavelength and scanning the frequency-doubled output of a tunable dye laser, laser induced fluorescence signals arising from collisional population of rotational levels within both dyads are observed and state-to-state rate constants for rotational relaxation are obtained. Rotational relaxation to J levels within the pumped (upper energy) Fermi-dyad accounts for 74% of the total rate of loss of the population of the J=12 level, whereas relaxation to J levels in its partner accounts for only 16%. A further 7% of the absolute rotational relaxation rate is accounted for by vibrational relaxation out of the mixed levels, leaving only 3%–4% of the total relaxation to be accounted for.


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