Table of Contents Author Guidelines Submit a Manuscript
Advances in Physical Chemistry
Volume 2012 (2012), Article ID 164752, 19 pages
Review Article

Constructing Potential Energy Surfaces for Polyatomic Systems: Recent Progress and New Problems

Departamento de Química Física, Universidad de Extremadura, 06071 Badajoz, Spain

Received 11 May 2011; Accepted 14 July 2011

Academic Editor: Laimutis Bytautas

Copyright © 2012 J. Espinosa-Garcia et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


Different methods of constructing potential energy surfaces in polyatomic systems are reviewed, with the emphasis put on fitting, interpolation, and analytical (defined by functional forms) approaches, based on quantum chemistry electronic structure calculations. The different approaches are reviewed first, followed by a comparison using the benchmark H + CH4 and the H + NH3 gas-phase hydrogen abstraction reactions. Different kinetics and dynamics properties are analyzed for these reactions and compared with the available experimental data, which permits one to estimate the advantages and disadvantages of each method. Finally, we analyze different problems with increasing difficulty in the potential energy construction: spin-orbit coupling, molecular size, and more complicated reactions with several maxima and minima, which test the soundness and general applicability of each method. We conclude that, although the field of small systems, typically atom-diatom, is mature, there still remains much work to be done in the field of polyatomic systems.