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

Journal Article · Tue Nov 01 00:00:00 EST 2005 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2102908· OSTI ID:20723192

Prakash, M K; Marcus, R A ^[1]

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

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.

• OSTI ID: 20723192
• Journal Information: Journal of Chemical Physics, Vol. 123, Issue 17; Other Information: DOI: 10.1063/1.2102908; (c) 2005 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
EQUILIBRIUM
FRACTIONATION
ISOTOPE EFFECTS
ISOTOPES
MASS DIFFERENCE
NITROUS OXIDE
PERTURBATION THEORY
PHOTOLYSIS
REACTION KINETICS
SPIN