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Title: Zero-point energy, tunneling, and vibrational adiabaticity in the Mu + H2 reaction

Abstract: Isotopic substitution of muonium for hydrogen provides an unparalleled opportunity to deepen our understanding of quantum mass effects on chemical reactions. A recent topical review [Aldegunde et al., Mol. Phys. 111, 3169 (2013)] of the thermal and vibrationally-stateselected reaction of Mu with H2 raises a number of issues that are addressed here. We show that some earlier quantum mechanical calculations of the Mu + H2 reaction, which are highlighted in this review and which have been used to benchmark approximate methods, are in error by as much as 19% in the low-temperature limit. We demonstrate that an approximate treatment of the Born–Oppenheimer diagonal correction that was used in some recent studies is not valid for treating the vibrationally-state-selected reaction. We also discuss why vibrationally adiabatic potentials that neglect bend zero-point energy are not a useful analytical tool for understanding reaction rates and why vibrationally nonadiabatic transitions cannot be understood by considering tunneling through vibrationally adiabatic potentials. Finally, we present calculations on a hierarchical family of potential energy surfaces to assess the sensitivity of rate constants to the quality of the potential surface.
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Resource Type:
Journal Article
Resource Relation:
Journal Name: Molecular Physics, 113(2):160-175
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
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Country of Publication:
United States
Born–Oppenheimer diagonal correction, kinetic isotope effects, tunneling, quantum