Deep tunneling in the unimolecular decay of CH3CHOO Criegee intermediates to OH radical products

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

doi:10.1063/1.4972015

Deep tunneling in the unimolecular decay of CH₃CHOO Criegee intermediates to OH radical products

Journal Article · Sun Dec 18 23:00:00 EST 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4972015· OSTI ID:1373744

Fang, Yi ^[1]; ^[1]; Barber, Victoria P. ^[1]; ^[2]; ^[3]; Lester, Marsha I. ^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemistry
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry

Unimolecular decay of Criegee intermediates produced in alkene ozonolysis is known to be a significant source of OH radicals in the troposphere. In this work, unimolecular decay of the methyl-substituted Criegee intermediate, syn-CH₃CHOO, to OH products is shown to occur at energies significantly below the transition state barrier for a 1,4 hydrogen transfer that leads to these products. The rate of appearance of OH products arising from tunneling through the barrier is obtained through direct time-domain measurements following the vibrational activation of syn-CH₃CHOO. IR excitation of syn-CH₃CHOO at energies nearly 2000 cm^-1 below the barrier is achieved through combination bands involving CH stretch and another lower frequency mode, and the resultant OH products are detected by UV laser-induced fluorescence. The observed syn-CH₃CHOO combination bands in the 4100–4350 cm^-1 region are identified by comparison with the computed IR absorption spectrum. The experimental decay rates are found to be ca. 106 s^-1 in this deep tunneling regime, which is approximately 100-times slower than that in the vicinity of the barrier.The experimental results are consistent with statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of the microcanonical decay rates with tunneling through the barrier, and notable deviations may originate from the sparsity in the density of states for syn-CH₃CHOO at lower energies. Finally, thermal unimolecular decay of syn-CH₃CHOO is predicted to have significant contribution from microcanonical rates at energies that are much below the barrier.

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 & Biosciences Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1373744

Alternate ID(s):: OSTI ID: 1336837

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 23 Vol. 145; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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