Improved free-energy interpolation scheme for obtaining gas-phase reaction rates from ring-polymer molecular dynamics

摘要

Quantum reaction rates for bimolecular gas-phase reactions can be computed efficiently and to a realistic degree of approximation by applying ring-polymer molecular dynamics within a free-energy interpolation scheme [R. Collepardo-Guevara, Y.V. Suleimanov, and D.E. Manolopoulos, J. Chem. Phys. 130, 174713 (2009)]. Here, we present modifications to this scheme which simplify the implementation of the method, and have the advantage of yielding directly the free-energy as a function of the interpolation coordinate. We also take the opportunity to verify the benchmark results obtained for the H + H₂ and Cl + HCl reactions by Collepardo-Guevara et al., obtaining excellent agreement for H + H₂ and reasonable agreement for Cl + HCl.View full textDownload full textKeywordsquantum dynamics, reaction rates, ring polymer molecular dynamics, molecular simulationRelated var addthis_config = { ui_cobrand: "Taylor & Francis Online", services_compact: "citeulike,netvibes,twitter,technorati,delicious,linkedin,facebook,stumbleupon,digg,google,more", pubid: "ra-4dff56cd6bb1830b" }; Add to shortlist Link Permalink http://dx.doi.org/10.1080/00268976.2012.666574