Path-integral virial estimator for reaction-rate calculation based on the quantum instanton approximation

The Journal of Chemical Physics
Sandy YangWilliam H Miller

Abstract

The quantum instanton approximation is a type of quantum transition-state theory that calculates the chemical reaction rate using the reactive flux correlation function and its low-order derivatives at time zero. Here we present several path-integral estimators for the latter quantities, which characterize the initial decay profile of the flux correlation function. As with the internal energy or heat-capacity calculation, different estimators yield different variances (and therefore different convergence properties) in a Monte Carlo calculation. Here we obtain a virial (-type) estimator by using a coordinate scaling procedure rather than integration by parts, which allows more computational benefits. We also consider two different methods for treating the flux operator, i.e., local-path and global-path approaches, in which the latter achieves a smaller variance at the cost of using second-order potential derivatives. Numerical tests are performed for a one-dimensional Eckart barrier and a model proton transfer reaction in a polar solvent, which illustrates the reduced variance of the virial estimator over the corresponding thermodynamic estimator.

References

Apr 25, 2002·Annual Review of Physical Chemistry·Jiali Gao, Donald G Truhlar
Jul 23, 2004·The Journal of Chemical Physics·Michele Ceotto, William H Miller
Jul 23, 2004·The Journal of Chemical Physics·Takeshi Yamamoto, William H Miller
Feb 9, 2005·Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics·Cristian Predescu
Mar 3, 2005·The Journal of Chemical Physics·Takeshi Yamamoto, William H Miller
Mar 3, 2005·The Journal of Chemical Physics·Michele CeottoWilliam H Miller
Apr 20, 2005·The Journal of Chemical Physics·Shilong Yang, Jianshu Cao
Aug 20, 2005·The Journal of Chemical Physics·Jirí VanícekF Javier Aoiz

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Citations

May 27, 2010·The Journal of Chemical Physics·Marcin Buchowiecki, Jirí Vanícek
Nov 23, 2015·The Journal of Chemical Physics·Konstantin Karandashev, Jiří Vaníček
Dec 29, 2017·Structural Dynamics·Konstantin KarandashevJeremy O Richardson
Nov 16, 2013·Physical Chemistry Chemical Physics : PCCP·Jing HuangMarkus Meuwly
Oct 17, 2019·The Journal of Chemical Physics·Christophe L VaillantJeremy O Richardson
Nov 10, 2006·Chemical Reviews·Antonio Fernandez-RamosDonald G Truhlar

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