Beyond transition state theory: accurate description of nuclear quantum effects on the rate and equilibrium constants of chemical reactions using Feynman path integrals.
Nuclear tunneling and other nuclear quantum effects have been shown to play a significant role in molecules as large as enzymes even at physiological temperatures. I discuss how these quantum phenomena can be accounted for rigorously using Feynman path integrals in calculations of the equilibrium and kinetic isotope effects as well as of the temperature dependence of the rate constant. Because these calculations are extremely computationally demanding, special attention is devoted to increasing the computational efficiency by orders of magnitude by employing efficient path integral estimators.
Laboratory of Theoretical Physical Chemistry, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, Avenue Forel, CH-1015 Lausanne. jiri.vanicek@epfl.ch
Jirí
J
Vanícek
D000466:Alkadienes / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D007554:Isotopes; D007700:Kinetics; D008432:Mathematical Computing; D008956:Models, Chemical; D008958:Models, Molecular; D010420:Pentanes / Q000737:chemistry; D011789:Quantum Theory; D013696:Temperature
D000466:Alkadienes; D007554:Isotopes; D010420:Pentanes; D006859:Hydrogen; C011970:1,3-pentadiene