Application of Interpolating Moving Least Squares Fitting to Hypervelocity Collision Dynamics: O(³P) + HCI

Abstract

We use an automated interpolating moving least-squares (IMLS) algorithm, which generates a fitted ab initio surface for systems of arbitrary topology, to construct a global ohcl (3A") surface at the UB3LYP/aug-cc- pvtz level of theory. This analytic PES includes all reaction channels and ohcl geometries with energies up to 144 kcal/mol (6.25 ev) above the O + hcl asymptote. The fitted surface was combined with the quasiclassical trajectory method to study the dynamics of the O( 3P) + hcl reaction at hyperthermal collision energies. The fitted PES greatly improves energy conservation during trajectory integration and eliminates problems with ab initio convergence, which are often encountered during direct dynamics studies. The more extensive trajectory calculations yield new insight into the title reaction and agree well with previous experimental studies and direct dynamics results.

Department(s)

Chemistry

Keywords and Phrases

Ab initio; Arbitrary topology; Direct dynamics; Experimental studies; Hyperthermal collisions; Hypervelocity collision; Interpolating moving least squares; Moving least squares; Quasi-classical trajectory method; Reaction channels; Trajectory calculations, Curve fitting; Energy conservation; Potential energy; Potential energy surfaces, Dynamics

International Standard Serial Number (ISSN)

1089-5639

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2009 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Apr 2009

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