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Abstract

This work suggests a connection between Landau-Zener transition probabilities between two crossing potentials in the classically accessible WKB regime and Landau-Lifshitz transition probabilities in the classically inaccessible WKB regime. It is based on the uniform Airy (UAi) approximation which represents a generalization of quantum transition probabilities for linear crossing potentials with constant coupling. The performance of the UAi approximation is tested by comparison with distorted-wave probabilities for an exponential potential model and illustrated for potentials that determine the intersection of two ab initio vibronic potential surfaces of the NO-Ar system.