A new accurate and full dimensional potential energy surface of H-5(+) based on a triatomics-in-molecules analytic functional form

作者：Aguado A; Barragan P; Prosmiti R; Delgado Barrio G; Villarreal P; Roncero O^*

来源：Journal of Chemical Physics, 2010, 133(2): 024306.

DOI：10.1063/1.3454658

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.

• 出版日期2010-7-14