Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets

Raston, Paul L.; Obi, Emmanuel I.; Douberly, Gary E.

doi:10.1021/acs.jpca.7b07906

Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets

Journal Article · Fri Sep 22 00:00:00 EDT 2017 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.7b07906· OSTI ID:1409064

^[1]; Obi, Emmanuel I. ^[2]; ^[2]

James Madison Univ., Harrisonburg, VA (United States); University of Georgia, Athens, GA
Univ. of Georgia, Athens, GA (United States)

Here, 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 linewidths of which provide information about the flow of vibrational energy in the complexes; vibrational lifetime broadening is prominent for OH–CH₄ and OD–CD₄, for which the excited OX stretching state has a nearby CY₄ stretching fundamental (X, Y = H or D).

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Georgia Research Foundation, Athens, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0008086

OSTI ID:: 1409064

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 40 Vol. 121; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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