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

Prakash, M. K. and Marcus, R. A. (2005) Three-isotope plot of fractionation in photolysis: A perturbation theoretical expression. Journal of Chemical Physics, 123 (17). Art. No. 174308. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:PRAjcp05

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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 N2O 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.


Item Type:Article
Additional Information:©2005 American Institute of Physics (Received 20 June 2005; accepted 9 September 2005; published online 31 October 2005) It is a pleasure to acknowledge the support of this research by the National Science Foundation.
Subject Keywords:nitrogen compounds; isotope effects; photodissociation; chemical exchanges; perturbation theory; reaction kinetics theory; chemical equilibrium
Record Number:CaltechAUTHORS:PRAjcp05
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:PRAjcp05
Alternative URL:http://dx.doi.org/10.1063/1.2102908
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:3074
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:12 May 2006
Last Modified:26 Dec 2012 08:52

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