TRANSITION VECTOR SYMMETRY AND THE INTERNAL PSEUDO-ROTATION AND INVERSION PATHS OF CLF4+

A new definition of the transition vector symmetry group is suggested. The utility of the definition is demonstrated by calculations of the pathways of the internal pseudo-rotation and inversion of ClF4+ (DZP a nd DZP/MP2 levels). The lowest internal pseudo-rotation proceeds by a Berry mechanism with an activation barrier of 6.7 kcal mol-1. The leve r mechanism has a higher barrier of 39.5 kcal mol-1 and would lead to more extensive fluorine scrambling. The inversion reaction that leads to enantiomerization corresponds to a planar D4h transition state with an activation barrier of 60 kcal mol-1.