title: Quantum-classical Liouville dynamics of proton and deuteron transfer rates in a solvated hydrogen-bonded complex.
abstract: Proton and deuteron transfer reactions in a hydrogen-bonded complex dissolved in a polar solution are studied using quantum-classical Liouville dynamics. Reactive-flux correlation functions that involve quantum-classical Liouville dynamics for species operators and quantum equilibrium sampling are used to calculate the rate constants. Adiabatic and nonadiabatic reaction rates are computed, compared, and analyzed. Large variations of the kinetic isotope effect (KIE) for this reaction have been observed in the literature, which depend on the nature of the approximate calculation used to estimate the proton and deuteron transfer rates. Our estimate of the KIE lies at the low end of the range of previously observed values, suggesting a rather small KIE for this reaction.
authors.affiliation: Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055 USA. hannag@umich.edu
authors.forename: Gabriel
authors.initials: G
authors.lastname: Hanna
authors.forename: Raymond
authors.initials: R
authors.lastname: Kapral
mesh_terms: D003198:Computer Simulation; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D046911:Macromolecular Substances / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D011522:Protons; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry*
chemical_list: D046911:Macromolecular Substances; D011522:Protons; D012997:Solvents; D006859:Hydrogen