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Title: Investigation of the two- and three-fragment photodissociation of the tert -butyl peroxy radical at 248 nm

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry, University of California, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1398133
Grant/Contract Number:
AC02-05CH11231
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 13; Related Information: CHORUS Timestamp: 2018-02-15 02:34:08; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Nichols, Bethan, Sullivan, Erin N., Ryazanov, Mikhail, Hong, Cynthia M., and Neumark, Daniel M. Investigation of the two- and three-fragment photodissociation of the tert -butyl peroxy radical at 248 nm. United States: N. p., 2017. Web. doi:10.1063/1.4994713.
Nichols, Bethan, Sullivan, Erin N., Ryazanov, Mikhail, Hong, Cynthia M., & Neumark, Daniel M. Investigation of the two- and three-fragment photodissociation of the tert -butyl peroxy radical at 248 nm. United States. doi:10.1063/1.4994713.
Nichols, Bethan, Sullivan, Erin N., Ryazanov, Mikhail, Hong, Cynthia M., and Neumark, Daniel M. Sat . "Investigation of the two- and three-fragment photodissociation of the tert -butyl peroxy radical at 248 nm". United States. doi:10.1063/1.4994713.
@article{osti_1398133,
title = {Investigation of the two- and three-fragment photodissociation of the tert -butyl peroxy radical at 248 nm},
author = {Nichols, Bethan and Sullivan, Erin N. and Ryazanov, Mikhail and Hong, Cynthia M. and Neumark, Daniel M.},
abstractNote = {},
doi = {10.1063/1.4994713},
journal = {Journal of Chemical Physics},
number = 13,
volume = 147,
place = {United States},
year = {Sat Oct 07 00:00:00 EDT 2017},
month = {Sat Oct 07 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on October 5, 2018
Publisher's Accepted Manuscript

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

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  • The photodissociation dynamics of the simplest alkyl peroxy radicals, methyl peroxy (CH 3OO) and ethyl peroxy C 2H 5OO , 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 leadingmore » 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.« less
  • Photodissociation of the group VIB (Cr,Mo,W) hexacarbonyls has been studied at 248 nm using molecular beam photofragment spectroscopy. One, two and three photon processes have been observed. Analysis of the product velocity distributions shows that the photodissociation mechanism consists of sequential CO eliminations with the {ital n}th photon channel best described as the single photon photodissociation of the stable products of the {ital n}-1st photon channel. The product translational energy distribution for the first CO elimination step is quantitatively similar for all three hexacarbonyls and characteristic of a repulsive translational energy release. The product translational energy distributions of all subsequentmore » CO elimination steps are accurately described by a simple, microcanonical model. Qualitative molecular orbital considerations suggest that the large product translational energy observed in the first CO elimination step results from a repulsive {sigma} interaction between the closed shell CO ligand and an excited molecular orbital which has a significant admixture of metal ({ital n}+1)p{sub z}, ({ital n}+1){ital s} and {ital nd}{sub {ital z}{sup 2}} orbitals. This repulsive interaction is absent in the remaining CO elimination steps because there are vacancies in the coordination shell along the {ital z} axis.« less
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