Accelerating quantum instanton calculations of the kinetic isotope effects

Abstract: Path integral implementation of the quantum instanton approximation currently belongs among the most accurate methods for computing quantum rate constants and kinetic isotope effects, but its use has been limited due to the rather high computational cost. Here we demonstrate that the efficiency of quantum instanton calculations of the kinetic isotope effects can be increased by orders of magnitude by combining two approaches: The convergence to the quantum limit is accelerated by employing high-order path integral factorizations of the Boltzmann operator, while the statistical convergence is improved by implementing virial estimators for relevant quantities. After deriving several new virial estimators for the high-order factorization and evaluating the resulting increase in efficiency, using $\mathrm{\cdot H_{\alpha}+H_{\beta}H_{\gamma}\rightarrow H_{\alpha}H_{\beta}+\cdot H_{\gamma }}$ reaction as an example, we apply the proposed method to obtain several kinetic isotope effects on $\mathrm{CH_{4}+\cdot H\rightleftharpoons\cdot CH_{3}+H_{2}}$ forward and backward reactions.