A LOWER-BOUND PROPERTY OF ADIABATIC PHASE SHIFTS

In molecular encounters, the total energy of the system may not be sufficient to enable any but the ground-state electronic surface to determine nuclear motions adiabatically. When this happens, non-adiabatic transitions are energetically forbidden. It is shown that for such collisions the phase shifts computed in the adiabatic approximation are lower bounds to the exact phase shifts. The proof derives from a study of the non-local potential which arises when the exact collision problem is transformed so as to involve only nuclear motion explicitly. Use is made of a well-known relation between magnitudes of effective potentials and of phase shifts associated with two respective hamiltonians [1, 2 (b)]. This result is related to a theorem by Hahn et al. [2 (a]. The similarities and differences between the two are discussed. © 1968 Taylor and Francis Group, LLC.