Journal of Physical Chemistry A, Vol.121, No.40, 7597-7602, 2017
Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets
The entrance channel complex in the exothermic OH + CH4 -> H2O + CH3 reaction has been isolated in helium nanodroplets following the sequential pick-up of the hydroxyl radical and methane. The a-type OH stretching band was probed with infrared depletion spectroscopy, revealing a spectrum qualitatively similar to that previously reported in the gas phase, but with additional substructure that is due to the different internal rotation states of methane (j(CH4) = 0, 1, or 2) in the complex. We fit the spectra by assuming the rotational constants of the complex are the same for all internal rotation states; however, subband origins are found to decrease with increasing j(CH4). Measurements of deuterated complexes have also been made (OD-CH4, OH-CD4, and OD-CD4), the relative linewidtlis of which provide, information about the flow of vibrational energy in the complexes; vibrational lifetime broadening is prominent for OH-CH, and OD-CD4, for which the excited OX stretchirig state has a nearby CY4 stretching fundamental (X, Y = H or D).