A semiclassical treatment of the l-j correlation in atom-diatom collisions

摘要

The explicit consideration of the vector correlations is an essential step when it comes to determining the mechanism of chemical reactions. Usual vector correlations involve initial and final relative velocity vectors and rotational angular momenta. However, the correlation between the orbital, l, and rotational, j, angular momenta has seldom received any attention. In this article, we present a semiclassical methodology capable of describing the l-j correlation that may serve as a connection between the quantum and quasiclassical treatments. Using the scattering matrix in the orbital angular momentum representation, the l-j correlation is expressed as a probability density function of the angle formed by both vectors. This technique is exemplified through the H + D-2 reaction and its accuracy is appraised by comparing with results derived from calculations based on quasiclassical trajectories. (C) 2015 AIP Publishing LLC.