skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Revisiting the photodissociation dynamics of the phenyl radical

Abstract

We have reinvestigated the photodissociation dynamics of the phenyl radical at 248 nm and 193 nm via photofragment translational spectroscopy under a variety of experimental conditions aimed at reducing the nascent internal energy of the phenyl radical and eliminating signal from contaminants. Under these optimized conditions, slower translational energy (P(E{sub T})) distributions for H-atom loss were seen at both wavelengths than in previously reported work. At 193 nm, the branching ratio for C{sub 2}H{sub 2} loss vs. H-atom loss was found to be 0.2 ± 0.1, a significantly lower value than was obtained previously in our laboratory. The new branching ratio agrees with calculated Rice-Ramsperger-Kassel-Marcus rate constants, suggesting that the photodissociation of the phenyl radical at 193 nm can be treated using statistical models. The effects of experimental conditions on the P(E{sub T}) distributions and product branching ratios are discussed.

Authors:
; ; ;  [1]
  1. Department of Chemistry, University of California, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)
Publication Date:
OSTI Identifier:
22308370
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 10; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOMS; DISSOCIATION; PHENYL RADICALS; PHOTOLYSIS; REACTION KINETICS; SIGNALS; SPECTROSCOPY; STATISTICAL MODELS; WAVELENGTHS

Citation Formats

Cole-Filipiak, Neil C., Shapero, Mark, Negru, Bogdan, and Neumark, Daniel M., E-mail: dneumark@berkeley.edu. Revisiting the photodissociation dynamics of the phenyl radical. United States: N. p., 2014. Web. doi:10.1063/1.4894398.
Cole-Filipiak, Neil C., Shapero, Mark, Negru, Bogdan, & Neumark, Daniel M., E-mail: dneumark@berkeley.edu. Revisiting the photodissociation dynamics of the phenyl radical. United States. doi:10.1063/1.4894398.
Cole-Filipiak, Neil C., Shapero, Mark, Negru, Bogdan, and Neumark, Daniel M., E-mail: dneumark@berkeley.edu. Sun . "Revisiting the photodissociation dynamics of the phenyl radical". United States. doi:10.1063/1.4894398.
@article{osti_22308370,
title = {Revisiting the photodissociation dynamics of the phenyl radical},
author = {Cole-Filipiak, Neil C. and Shapero, Mark and Negru, Bogdan and Neumark, Daniel M., E-mail: dneumark@berkeley.edu},
abstractNote = {We have reinvestigated the photodissociation dynamics of the phenyl radical at 248 nm and 193 nm via photofragment translational spectroscopy under a variety of experimental conditions aimed at reducing the nascent internal energy of the phenyl radical and eliminating signal from contaminants. Under these optimized conditions, slower translational energy (P(E{sub T})) distributions for H-atom loss were seen at both wavelengths than in previously reported work. At 193 nm, the branching ratio for C{sub 2}H{sub 2} loss vs. H-atom loss was found to be 0.2 ± 0.1, a significantly lower value than was obtained previously in our laboratory. The new branching ratio agrees with calculated Rice-Ramsperger-Kassel-Marcus rate constants, suggesting that the photodissociation of the phenyl radical at 193 nm can be treated using statistical models. The effects of experimental conditions on the P(E{sub T}) distributions and product branching ratios are discussed.},
doi = {10.1063/1.4894398},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 10,
volume = 141,
place = {United States},
year = {2014},
month = {9}
}