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Title: Accelerating quantum instanton calculations of the kinetic isotope effects

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 ⋅H{sub α} + H{sub β}H{sub γ} → H{sub α}H{sub β} + ⋅ H{sub γ} reaction as an example, we apply the proposed method to obtain several kinetic isotope effects on CH{sub 4} + ⋅ H ⇌ ⋅ CH{sub 3} + H{sub 2} forward and backward reactions.
Authors:
;  [1]
  1. Laboratory of Theoretical Physical Chemistry, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne CH-1015 (Switzerland)
Publication Date:
OSTI Identifier:
22493244
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 19; Other Information: (c) 2015 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CONVERGENCE; EFFICIENCY; FACTORIZATION; HYDROGEN; IMPLEMENTATION; INSTANTONS; ISOTOPE EFFECTS; METHANE; PATH INTEGRALS; REACTION KINETICS