Efficient estimators for quantum instanton evaluation of the kinetic isotope effects: application to the intramolecular hydrogen transfer in pentadiene.
The quantum instanton approximation is used to compute kinetic isotope effects for intramolecular hydrogen transfer in cis-1,3-pentadiene. Due to the importance of skeleton motions, this system with 13 atoms is a simple prototype for hydrogen transfer in enzymatic reactions. The calculation is carried out using thermodynamic integration with respect to the mass of the isotopes and a path integral Monte Carlo evaluation of relevant thermodynamic quantities. Efficient "virial" estimators are derived for the logarithmic derivatives of the partition function and the delta-delta correlation functions. These estimators require significantly fewer Monte Carlo samples since their statistical error does not increase with the number of discrete time slices in the path integral. The calculation treats all 39 degrees of freedom quantum mechanically and uses an empirical valence bond potential based on a molecular mechanics force field.
Vanícek
Jirí
J
Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California, Berkeley, California 94720, USA. vanicek@post.harvard.edu
Miller
William H
WH
D000466:Alkadienes / Q000737:chemistry; D002627:Chemistry, Physical / Q000379:methods; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D015233:Models, Statistical; D008962:Models, Theoretical; D009010:Monte Carlo Method; D016011:Normal Distribution; D011789:Quantum Theory; D013499:Surface Properties; D013816:Thermodynamics
D000466:Alkadienes; D006859:Hydrogen