Photodissociation dynamics of the simplest alkyl peroxy radicals, CH3OO and C2H5OO, at 248 nm

Sullivan, Erin N.; Nichols, Bethan; Neumark, Daniel M.

doi:10.1063/1.5011985

Title: Photodissociation dynamics of the simplest alkyl peroxy radicals, CH₃OO and C₂H₅OO, at 248 nm

Journal Article · Sun Jan 28 00:00:00 EST 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5011985· OSTI ID:1435113

Sullivan, Erin N. ^[1]; Nichols, Bethan ^[1];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

The photodissociation dynamics of the simplest alkyl peroxy radicals, methyl peroxy (CH₃OO) and ethyl peroxy C₂H₅OO^{, are investigated using fast beam photofragment translational spectroscopy. A fast beam of CH₃OO^- or C₂H₅OO^- anions is photodetached to generate neutral radicals that are subsequently dissociated using 248 nm photons. The coincident detection of the photofragment positions and arrival times allows for the determination of mass, translational energy, and angular distributions for both two-body and three-body dissociation events. CH₃OO exhibits repulsive O loss resulting in the formation of O(¹D) + CH₃O with high translational energy release. Minor two-body channels leading to OH + CH₂O and CH₃O + O(³P) formation are also detected. In addition, small amounts of H + O(₃P) + CH₂O are observed and attributed to O loss followed by CH₃O dissociation. C₂H₅OO exhibits more complex dissociation dynamics, in which O loss and OH loss occur in roughly equivalent amounts with O(¹D) formed as the dominant O atom electronic state via dissociation on a repulsive surface. Minor two-body channels leading to the formation of O₂ + C₂H₅ and HO₂ + C₂H₄ are also observed and attributed to a ground state dissociation pathway following internal conversion. Additionally, C₂H₅OO^{dissociation yields a three-body product channel, CH₃ + O(³P) + CH₂O, for which the proposed mechanism is repulsive O loss followed by the dissociation of C₂H₅O over a barrier. These results are compared to a recent study of tert-butyl peroxy (t-BuOO) in which 248 nm excitation results in three-body dissociatio n and ground state two-body dissociation but no O(¹D) production.}}

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1435113

Alternate ID(s):: OSTI ID: 1418187

Journal Information:: Journal of Chemical Physics, Vol. 148, Issue 4; Related Information: © 2018 Author(s).; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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