title: Can quasiclassical trajectory calculations reproduce the extreme kinetic isotope effect observed in the muonic isotopologues of the H + H2 reaction?
abstract: Rate coefficients for the mass extreme isotopologues of the H + H(2) reaction, namely, Mu + H(2), where Mu is muonium, and Heμ + H(2), where Heμ is a He atom in which one of the electrons has been replaced by a negative muon, have been calculated in the 200-1000 K temperature range by means of accurate quantum mechanical (QM) and quasiclassical trajectory (QCT) calculations and compared with the experimental and theoretical results recently reported by Fleming et al. [Science 331, 448 (2011)]. The QCT calculations can reproduce the experimental and QM rate coefficients and kinetic isotope effect (KIE), k(Mu)(T)/k(Heμ)(T), if the Gaussian binning procedure (QCT-GB)--weighting the trajectories according to their proximity to the right quantal vibrational action--is applied. The analysis of the results shows that the large zero point energy of the MuH product is the key factor for the large KIE observed.
authors.affiliation: Departamento de Química Física, Facultad de Química, Universidad Complutense, 28040 Madrid, Spain.
authors.forename: P G
authors.initials: PG
authors.lastname: Jambrina
authors.forename: Ernesto
authors.initials: E
authors.lastname: García
authors.forename: Víctor J
authors.initials: VJ
authors.lastname: Herrero
authors.forename: Vicente
authors.initials: V
authors.lastname: Sáez-Rábanos
authors.forename: F J
authors.initials: FJ
authors.lastname: Aoiz