Comparison between static and adiabatic coupling mechanisms for nonradiative multiphonon transitions in semiclassical approximation I. Tunnelling at small relaxation

摘要: Basic equations of the perturbational theory nonradiative multiphonon transitions are reformulated in semiclassical approximation. They specialized for mechanisms static (diabatic) and adiabatic coupling corresponding to polar alternatives crossing versus non-crossing oscillator potentials a two-level-one-mode system. Tunnelling rates calculated on basis contour integrals complex co-ordinate plane. These proportional square off-diagonal electron-oscillator interaction as commonly expected. For alternative we have obtained non-monotonous (oscillating) pre-exponential transition rate factor. This unfamiliar result is based certain “beyondnon-Condon” procedure consisting consequent observation both familiarnon-Condon effect represented by Lorentz function behaviour non-adiabaticity term associatedavoided- (hyperbolic) classical region. Present results confirm general non-equivalence asymptotic approach between mechanism-specific tunnelling at small interactions.