Stress Test for Quantum Dynamics Approximations: Deep Tunneling in the Muonium Exchange Reaction D + HMu → DMu + H

• Published in: The journal of physical chemistry letters 2014-12, Vol.5 (23), p.4219-4224
• Main Authors: Pérez de Tudela, Ricardo, Suleimanov, Yury V, Richardson, Jeremy O, Sáez Rábanos, Vicente, Green, William H, Aoiz, F. J
• Format: Article
• Language: English
• Subjects: Kinetics and Dynamics
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/jz502216g

Quantum effects play a crucial role in chemical reactions involving light atoms at low temperatures, especially when a light particle is exchanged between two heavier partners. Different theoretical methodologies have been developed in the last decades attempting to describe zero-point energy and tunneling effects without abandoning a classical or semiclassical framework. In this work, we have chosen the D + HMu → DMu + H reaction as a stress test system for three well-established methods: two representative versions of transition state theory (TST), canonical variational theory and semiclassical instanton, and ring polymer molecular dynamics (RPMD). These calculations will be compared with accurate quantum mechanical results. Despite its apparent simplicity, the exchange of the extremely light muonium atom (0.114 u) becomes a most challenging reaction for conventional methods. The main result of this work is that RPMD provides an overall better performance than TST-based methods for such a demanding reaction. RPMD might well turn out to be a useful tool beyond TST applicability.