A Ring Polymer Molecular Dynamics Approach to Study the Transition between Statistical and Direct Mechanisms in the H-2 + H-3(+) -> H-3(+) + H-2 Reaction

作者：Suleimanov Yury V; Aguado Alfredo; Gomez Carrasco Susana; Roncero Octavio^*

来源：Journal of Physical Chemistry Letters, 2018, 9(9): 2133-2137.

DOI：10.1021/acs.jpclett.8b00783

Because of its fundamental importance in astrochemistry, the H-2 + H-3(+) -> H-3(+) + H-2 reaction has been studied experimentally in a wide temperature range. Theoretical studies of the title reaction significantly lag primarily because of the challenges associated with the proper treatment of the zero-point energy (ZPE). As a result, all previous theoretical estimates for the ratio between a direct proton-hop and indirect exchange (via the H-5(+) complex) channels deviate from the experiment, in particular, at lower temperatures where the quantum effects dominate. In this work, the ring polymer molecular dynamics (RPMD) method is applied to study this reaction, providing very good agreement with the experiment. RPMD is immune to the shortcomings associated with the ZPE leakage and is able to describe the transition from direct to indirect mechanisms below room temperature. We argue that RPMD represents a useful tool for further studies of numerous ZPE-sensitive chemical reactions that are of high interest in astrochemistry.

• 出版日期2018-5-3