Tunneling effects in the unimolecular decay of (CH3)2COO Criegee intermediates to OH radical products

Fang, Yi; Barber, Victoria P.; Klippenstein, Stephen J.; McCoy, Anne B.; Lester, Marsha I.

doi:10.1063/1.4979297

Tunneling effects in the unimolecular decay of (CH₃)₂COO Criegee intermediates to OH radical products

Journal Article · Tue Apr 04 00:00:00 EDT 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4979297· OSTI ID:1371548

^[1]; Barber, Victoria P. ^[1]; ^[2]; ^[3]; ^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Washington, Seattle, WA (United States)

Unimolecular decay of the dimethyl substituted Criegee intermediate (CH₃)₂COO is observed at energies significantly below the transition state barrier associated with hydrogen atom transfer with time-resolved detection of the resultant OH radical products. (CH₃)₂COO is prepared at specific energies in the 3900-4600 cm^-1 region through IR excitation of combination bands involving CH stretch and another lower frequency mode, and the OH products are detected by UV laser-induced fluorescence. OH appearance times on the order of microseconds are observed in this deep tunneling regime, which are about 100 times slower than that in the vicinity of the barrier. The experimental rates are in good accord with Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical dissociation rates for (CH₃)₂COO that include tunneling. Master equation modeling based on these microcanonical rates is used to predict the thermal decay rate of (CH₃)₂COO to OH products under atmospheric conditions of 276 s^-1 at 298 K (high pressure limit). Furthermore, thermal unimolecular decay of (CH₃)₂COO to OH products is shown to have significant contributions from tunneling at energies much below the barrier to H-atom transfer.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1371548

Alternate ID(s):: OSTI ID: 1361798

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 146; ISSN JCPSA6; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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