NONEMPIRICAL DYNAMICAL DFT CALCULATION OF THE BERRY PSEUDOROTATION OFPF5

The pseudo rotation of PF5 has been investigated using both static and dynamic density functional theory (DFT) methods. The lowest energy pa th is the Berry pseudorotation, corresponding to the concerted exchang e of two apical and two equatorial ligands. The potential energy surfa ce has been derived and the transition state localised. In ab initio m olecular dynamics the Berry pseudorotation has been observed and occur s with a typical period of 0.6 ps at 750 K. Analysis of the trajectori es and comparison of the spectral density with the vibrational frequen cies is presented.