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

Autor:	Jon P. Camden, Richard Dawes, Donald L. Thompson
Rok vydání:	2009
Předmět:	Surface (mathematics) Physics Yield (chemistry) Convergence (routing) Ab initio Physics::Chemical Physics Physical and Theoretical Chemistry Atomic physics Asymptote Moving least squares Potential energy Trajectory (fluid mechanics)
Zdroj:	The Journal of Physical Chemistry A. 113:4626-4630
ISSN:	1520-5215 1089-5639
DOI:	10.1021/jp8113144
Popis:	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 ((3)A'') 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((3)P) + 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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::8378fca291e8a20195dc147c5aeb6f9e https://doi.org/10.1021/jp8113144 Zobrazit plný text záznamu