Three-isotope plot of fractionation in photolysis: A perturbation theoretical expression

Prakash, M K; Marcus, R A

doi:10.1063/1.2102908

Title: Three-isotope plot of fractionation in photolysis: A perturbation theoretical expression

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Abstract

The slope of the three-isotope plot for the isotopomer fractionation by direct or nearly direct photodissociation is obtained using a perturbation theoretical analysis. This result, correct to first order in the mass difference, is the same as that for equilibrium chemical exchange reactions, a similarity unexpected a priori. A comparison is made with computational results for N{sub 2}O photodissociation. This theoretical slope for mass-dependent photolytic fractionation can be used to analyze the data for isotopic anomalies in spin-allowed photodissociation reactions. Earlier work on chemical equilibria is extended by avoiding a high-temperature approximation.

Authors:

Prakash, M K; Marcus, R A ^[1]

Noyes Laboratory of Chemical Physics MC 127-72, California Institute of Technology, Pasadena, California 91125 (United States)

Publication Date:: Tue Nov 01 00:00:00 EST 2005

OSTI Identifier:: 20723192

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 123; Journal Issue: 17; Other Information: DOI: 10.1063/1.2102908; (c) 2005 American Institute of Physics; 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; EQUILIBRIUM; FRACTIONATION; ISOTOPE EFFECTS; ISOTOPES; MASS DIFFERENCE; NITROUS OXIDE; PERTURBATION THEORY; PHOTOLYSIS; REACTION KINETICS; SPIN

Citation Formats


                    Prakash, M K, and Marcus, R A. Three-isotope plot of fractionation in photolysis: A perturbation theoretical expression.  United States: N. p., 2005. 
        Web.  doi:10.1063/1.2102908.

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                    Prakash, M K, & Marcus, R A. Three-isotope plot of fractionation in photolysis: A perturbation theoretical expression.  United States.  https://doi.org/10.1063/1.2102908

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                    Prakash, M K, and Marcus, R A. 2005.  
        "Three-isotope plot of fractionation in photolysis: A perturbation theoretical expression".  United States.  https://doi.org/10.1063/1.2102908.

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@article{osti_20723192,

  title        = {Three-isotope plot of fractionation in photolysis: A perturbation theoretical expression},

  author       = {Prakash, M K and Marcus, R A},

  abstractNote = {The slope of the three-isotope plot for the isotopomer fractionation by direct or nearly direct photodissociation is obtained using a perturbation theoretical analysis. This result, correct to first order in the mass difference, is the same as that for equilibrium chemical exchange reactions, a similarity unexpected a priori. A comparison is made with computational results for N{sub 2}O photodissociation. This theoretical slope for mass-dependent photolytic fractionation can be used to analyze the data for isotopic anomalies in spin-allowed photodissociation reactions. Earlier work on chemical equilibria is extended by avoiding a high-temperature approximation.},

  doi          = {10.1063/1.2102908},

  url          = {https://www.osti.gov/biblio/20723192},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 17,

  volume       = 123,

  place        = {United States},

  year         = {Tue Nov 01 00:00:00 EST 2005},

  month        = {Tue Nov 01 00:00:00 EST 2005}

}

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