Semiclassical analysis of the quantum instanton approximation.

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 be obtained directly from the semiclassical limit of the quantum instanton only 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.