Elaborating transition interface sampling methods (Q1780674)

The need for detailed atomistic information through molecular simulation for the kinetics of processes in complex environment, when it is not easily experimentally accessible, has given rise to two new efficient methods for calculating rate constants. The calculation of reaction rate constants by computer simulation requires an expression for the rate constant in terms of microscopic properties. In transition path sampling (TPS) the rate constant is taken from a time derivative of a correlation function, while the transition interface sampling approach (TIS) measures a reactive flux through multiple dividing surfaces. The second method is a partial path of TIS (PPTIS), which mainly exploits the loss of long time correlation. The two new techniques TIS and PPTIS are compared according to their efficiency and their relation to TST-based methods is examined. TIS can be considered as an improvement upon the original TPS, while PPTIS improves the efficiency but relies on the assumption of memory loss between interfaces. The efficiency of both methods should be tested further by detailed simulation.