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

Abstract

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,more » 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.« less

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1435113
Alternate Identifier(s):
OSTI ID: 1418187
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 4; Related Information: © 2018 Author(s).; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sullivan, Erin N., Nichols, Bethan, and Neumark, Daniel M. Photodissociation dynamics of the simplest alkyl peroxy radicals, CH3OO and C2H5OO, at 248 nm. United States: N. p., 2018. Web. doi:10.1063/1.5011985.
Sullivan, Erin N., Nichols, Bethan, & Neumark, Daniel M. Photodissociation dynamics of the simplest alkyl peroxy radicals, CH3OO and C2H5OO, at 248 nm. United States. doi:10.1063/1.5011985.
Sullivan, Erin N., Nichols, Bethan, and Neumark, Daniel M. Sun . "Photodissociation dynamics of the simplest alkyl peroxy radicals, CH3OO and C2H5OO, at 248 nm". United States. doi:10.1063/1.5011985. https://www.osti.gov/servlets/purl/1435113.
@article{osti_1435113,
title = {Photodissociation dynamics of the simplest alkyl peroxy radicals, CH3OO and C2H5OO, at 248 nm},
author = {Sullivan, Erin N. and Nichols, Bethan and Neumark, Daniel M.},
abstractNote = {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.},
doi = {10.1063/1.5011985},
journal = {Journal of Chemical Physics},
number = 4,
volume = 148,
place = {United States},
year = {2018},
month = {1}
}

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Figures / Tables:

Figure 1 Figure 1: Potential energy surface for CH3OO in which product asymptotic energies were determined using experimental heats of formation while transition state energies and structures were taken from Ref. 30. The red portion depicts pathways on the à state surface. Geometries were optimized using B3LYP/6-311G(d,p), and energies were calculated usingmore » the G2M method for all structures except those leading to channel 4A formation. Information regarding channel 4A was acquired from Ref. 24 in which the energies were calculated using MP3/6-31G∗∗ and the geometries optimized using UHF 6-31G∗∗. Product mass channels are defined in blue. The purple arrow represents the energy of a 248-nm photon, 5.00 eV, and the green arrow represents the energy of E$\mathbb R\atop{int}$, 0.28 eV.« less

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