A semianalytic model for photo-induced isotopic fractionation in simple molecules

Abstract

We have developed a semianalytic model for computing the photo-induced isotopic fractionation in simple molecules of interest to the atmospheric science community. The method is based on the Born-Oppenheimer approximation and the Reflection Principle. It has the main advantage of using commonly available input data, namely, the photolysis cross sections for the standard isotopologue/isotopomer and the ground state isotope-specific spectroscopic constants. The isotopic fractionation arises principally from the spectral shift induced by the small difference in zero point energy between isotopologues/isotopomers and the contraction of the wave function due to heavier isotope substitution. The latter effect dominates photolytic fractionation away from the cross section maxima. Our new approach is demonstrated with applications to the diatomic molecules HCl and HI, and the triatomic molecules N2O and O3. Agreement between the model and measurements is excellent. New modeling results for the fractionation of 15N15N16O in the stratosphere using the Caltech/JPL two-dimensional model are presented. Copyright 2004 by the American Geophysical Union.