Abstract

At sufficiently low temperatures, the reaction rates in solids are controlled by quantum rather than by thermal fluctuations. We solve the Schrödinger equation for a Gaussian wave packet in a non-stationary harmonic oscillator and derive simple analytical expressions for the increase of its mean energy with time induced by the time-periodic modulation. Applying these expressions to the modified Kramers theory, we demonstrate a strong increase of the rate of escape out of a potential well under the time-periodic driving, when the driving frequency of the well position equals its eigenfrequency, or when the driving frequency of the well width exceeds its eigenfrequency by a factor of [Formula: see text]. Such regimes can be realized near localized anharmonic vibrations (LAVs), in which the amplitude of atomic oscillations greatly exceeds that of harmonic oscillations (phonons) that determine the system temperature. LAVs can be excited either thermally or by external triggering, which can result in strong catalytic effects due to amplification of the Kramers rate.

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