Chemical Reaction Rates from Ring Polymer Molecular Dynamics: Zero Point Energy Conservation in Mu + H2 → MuH + H.
A fundamental issue in the field of reaction dynamics is the inclusion of the quantum mechanical (QM) effects such as zero point energy (ZPE) and tunneling in molecular dynamics simulations, and in particular in the calculation of chemical reaction rates. In this work we study the chemical reaction between a muonium atom and a hydrogen molecule. The recently developed ring polymer molecular dynamics (RPMD) technique is used, and the results are compared with those of other methods. For this reaction, the thermal rate coefficients calculated with RPMD are found to be in excellent agreement with the results of an accurate QM calculation. The very minor discrepancies are within the convergence error even at very low temperatures. This exceptionally good agreement can be attributed to the dominant role of ZPE in the reaction, which is accounted for extremely well by RPMD. Tunneling only plays a minor role in the reaction.
†Departamento de Química Física I, Facultad de CC. Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain.
Ricardo
R
Pérez de Tudela
†Departamento de Química Física I, Facultad de CC. Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain.
F J
FJ
Aoiz
‡Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.
Yury V
YV
Suleimanov
‡Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.
David E
DE
Manolopoulos
muonium; quantum mechanical calculations; ring polymer molecular dynamics; zero point energy