Uniform Semiclassical Instanton Rate Theory

[Image: see text] The instanton expression for the thermal transmission probability through a one-dimensional barrier is derived by using the uniform semiclassical energy-dependent transmission coefficient of Kemble. The resulting theory does not diverge at the “crossover temperature” but changes smoothly. The temperature-dependent energy of the instanton is the same as the barrier height when ℏβω(‡) = π and not 2π as in the “standard” instanton theory. The concept of a crossover temperature between tunneling and thermal activation, based on the divergence of the instanton rate, is obsolete. The theory is improved by assuring that at high energy when the energy-dependent transmission coefficient approaches unity the integrand decays exponentially as dictated by the Boltzmann factor and not as a Gaussian. This ensures that at sufficiently high temperatures the uniform theory reduces to the classical. Application to Eckart barriers demonstrates that the uniform theory provides a good estimate of the numerically exact result over the whole temperature range.