More efficient path-integral estimator for quantum instanton reaction rate calculation

PHYS 442

Sandy Yang,, Department of Chemistry, University of Illinois, Urbana, IL 61801, Takeshi Yamamoto,, Department of Chemistry, Kyoto University, Kyoto, Japan, and William H. Miller,, Department of Chemistry, University of California, Berkeley, CA 94720.
The quantum instanton (QI) model is a type of quantum transition state theory (QTST) that calculates the chemical reaction rate using the reactive flux correlation function and its low order derivatives at time zero. Some new and more efficient path-integral estimators for the latter quantities are presented here, which yield better variances (and therefore faster convergence properties) in a Monte Carlo calculation, and thus allows more computational benefits. Numerical tests are performed for a one-dimensional Eckart barrier and a model proton transfer reaction in a polar solvent.

Poster Session
7:30 PM-10:00 PM, Wednesday, 13 September 2006 Moscone Center -- Hall D, Poster

Division of Physical Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006