Vibrational predissociation (VP) of van der Waals complexes occurs via an isolated resonance. An isolated resonance possesses no classical counterpart. And yet, classical calculations of the decay yield the rates that are sometimes not too different from the quantum rates. We resolve this puzzle by addressing the following points: i) Quantum theory of VP: accurate and perturbative approaches; ii) Quasiclassical theory of VP: Landau method and recovery of VP transition probabilities from the correspondence principle transition probabilities; iii) Classical theory of VP: diffusional description of long-time chaotic dynamics. We calculate the ratio of the classical to quantum VP rates, determine the conditions when the rates of quantum dynamical tunneling is close to the classical diffusional rates across the chaotic sea and establish a classical counterpart of quantum perturbation approach.
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机译：van der WaaS复合物的振动预测（vp）通过孤立的共振发生。孤立的共振没有经典的同行。然而，衰减的经典计算产生的速率有时与量子率不同。我们通过解决以下几点来解决这个难题：i）vp的量子理论：准确和扰动的方法; ii）VP的拟流理论：LANDAU方法和VP转换概率从对应原理转换概率的回收; III）VP的经典理论：长时间混沌动力学的扩散描述。我们计算经典与量子VP速率的比率，确定量子动态隧道速率靠近混沌海域的经典扩散速率的条件，并建立量子扰动方法的经典对应。
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