Semiclassical analysis of the quantum instanton approximation

Abstract

We explore the relation between the quantum and semiclassical instanton approximations for the reaction rate constant. From the quantum instanton expression, we analyze the contributions to the rate constant in terms of minimum-action paths and find that two such paths dominate the expression. For symmetric barriers, these two paths join together to describe the semiclassical instanton periodic orbit. However, for asymmetric barriers, one of the two paths takes an unphysically low energy and dominates the expression, leading to order-of-magnitude errors in the rate predictions. Nevertheless, semiclassical instanton theory remains accurate. We conclude that semiclassical instanton theory can only be obtained directly from the semiclassical limit of the quantum instanton for symmetric systems. We suggest a modification of the quantum instanton approach which avoids sampling the spurious path and thus has a stronger connection to semiclassical instanton theory, giving numerically accurate predictions even for very asymmetric systems in the low temperature limit.

15 pages, 6 figures, accepted version

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Cited by in corpus (7)

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• Nonadiabatic instanton rate theory beyond the golden-rule limit
• Nonadiabatic quantum transition-state theory in the golden-rule limit. II. Overcoming the pitfalls of the saddle-point and semiclassical approximations
• Revisiting nuclear tunnelling in the aqueous ferrous-ferric electron transfer
• An improved path-integral method for golden-rule rates
• Semiclassical instanton theory for reaction rates at any temperature: How a rigorous real-time derivation solves the crossover temperature problem
• A general non-adiabatic quantum instanton approximation