Construction of an accurate potential energy surface by interpolation for quantum dynamics studies of a three-body system

Abstract

A method to construct an accurate potential energy surface ͑PES͒ by interpolation for a three-body reaction which is suitable for quantum dynamics studies is presented using ClϩH 2˜H ClϩH as an example. Use of the exponential coordinates led to a significant improvement. Dynamics results, both classical and quantal, on the LEPS and LEPS-interpolated PESs were nearly indistinguishable. An accurate analytic PES can be constructed with the ab initio results also, as manifested with the PES contours.

Modeling the Kinetics of Bimolecular Reactions

“…Especially for interpolation, the distinction between these kinds of fits and interpolations is not, however, as clear-cut as it might first seem because in all methods the interpolation or fit is a stronger function of nearby data than far away data, and as the dependence on distance away becomes steeper, a method becomes more local. In recent years, the increasing accuracy of WFT calculations for small systems has been responsible for the appearance of many interpolation algorithms. − …”