Quantum-classical Liouville dynamics of proton and deuteron transfer rates in a solvated hydrogen-bonded complex

URL:

https://www.scopus.com/inward/record.uri?eid=2-s2.0-42949157225&doi=10.1063%2f1.2907847&partnerID=40&md5=a3726575869fb884984de3c15cbf8841

Keywords:

Article, Chemical, chemical model, chemical structure, chemistry, Computer Simulation, Correlation methods, Deuteron, Deuteron transfer, hydrogen, hydrogen bond, Hydrogen Bonding, Isotopes, Kinetic isotope effect (KIE), Kinetics, Macromolecular Substances, macromolecule, Models, Molecular, Phase equilibria, proton, Protons, Quantum chemistry, Quantum Theory, Reaction rates, solvent, Solvents

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. © 2008 American Institute of Physics.