Quantum phase space theory for the calculation of v{center_dot}j vector correlations

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The quantum state-counting phase space theory commonly used to describe barrierless dissociation is recast in a helicity basis to calculate photofragment v{center_dot}j correlations. Counting pairs of fragment states with specific angular momentum projection numbers on the relative velocity provides a simple connection between angular momentum conservation and the v{center_dot}j correlation, which is not so evident in the conventional basis for phase space state counts. The upper bound on the orbital angular momentum, l, imposed by the centrifugal barrier cannot be included simply in the helicity basis, where l is not a good quantum number. Two approaches for a quantum calculation … continued below

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8 p.

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Hall, G. E. July 1, 1995.

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  • Hall, G. E. Brookhaven National Lab., Upton, NY (United States). Dept. of Chemistry

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The quantum state-counting phase space theory commonly used to describe barrierless dissociation is recast in a helicity basis to calculate photofragment v{center_dot}j correlations. Counting pairs of fragment states with specific angular momentum projection numbers on the relative velocity provides a simple connection between angular momentum conservation and the v{center_dot}j correlation, which is not so evident in the conventional basis for phase space state counts. The upper bound on the orbital angular momentum, l, imposed by the centrifugal barrier cannot be included simply in the helicity basis, where l is not a good quantum number. Two approaches for a quantum calculation of the v{center_dot}j correlation are described to address this point. An application to the photodissociation of NCCN is consistent with recent classical phase space calculations of Cline and Klippenstein. The observed vector correlation exceeds the phase space theory prediction. The authors take this as evidence of incomplete mixing of the K states of the linear parent molecule at the transition state, corresponding to an evolution of the body-fixed projection number K into the total helicity of the fragment pair state. The average over a thermal distribution of parent angular momentum in the special case of a linear molecule does not significantly reduce the v{center_dot}j correlation below that computed for total J = 0.

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8 p.

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INIS; OSTI as DE95014450

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  • 40. annual meeting of the Society of Photo-Optical Instrumentation Engineers, San Diego, CA (United States), 9-14 Jul 1995

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  • Other: DE95014450
  • Report No.: BNL--61928
  • Report No.: CONF-950793--5
  • Grant Number: AC02-76CH00016
  • Office of Scientific & Technical Information Report Number: 86979
  • Archival Resource Key: ark:/67531/metadc793094

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  • July 1, 1995

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  • Dec. 19, 2015, 7:14 p.m.

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  • Dec. 9, 2020, 2:34 p.m.

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Hall, G. E. Quantum phase space theory for the calculation of v{center_dot}j vector correlations, article, July 1, 1995; Upton, New York. (https://digital.library.unt.edu/ark:/67531/metadc793094/: accessed April 24, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.

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