Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 133, Issue 2, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.3454658
Keywords
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Funding
- Ministerio de Ciencia e Innovacion [CTQ2007-62898, CTQ2007-63332, FIS2007-62006, CSD2009-00038]
- Comunidad Autonoma de Madrid [S-2009/MAT-1467]
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In this work a reliable full nine-dimensional potential energy surface for studying the dynamics of H-5(+) is constructed, which is completely symmetric under any permutation of the nuclei. For this purpose, we develop a triatoms-in-molecules method as an extension of the more common diatoms-in-molecules one, which allows a very accurate description of the asymptotic regions by including correctly the charge-induced dipole and quadrupole interactions. Moreover, this treatment provides a semiquantitative description of all the topological features of the global potential compared with coupled cluster results. In particular, the hop of the proton between two H-2 fragments produces a double well in the potential. This resonant structure involving the five atoms produces a stabilization, lowering the barrier, and the triatoms-in-molecules yields to a barrier significantly higher than the ab initio results. Therefore, to improve the triatomics-in-molecules potential surface, two five-body terms are added, which are fitted to more than 110 000 coupled-cluster ab initio points. The global potential energy surface thus obtained in this work has an overall root mean square error of 0.079 kcal/mol for energies below 27 kcal/mol above the global well. The features of the potential are described and compared with previous available surfaces. (C) 2010 American Institute of Physics. [doi:10.1063/1.3454658]
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