Non-empirical dynamical DFT calculation of the Berry pseudorotation of PF5

The pseudo rotation of PF5 has been investigated using both static and dynamic density functional theory (DFT) methods. The lowest energy path is the Berry pseudorotation, corresponding to the concerted exchange of two apical and two equatorial ligands. The potential energy surface has been derived and the transition state localised. In ab initio molecular dynamics the Berry pseudorotation has been observed and occurs with a typical period of 0.6 ps at 750 K. Analysis of the trajectories and comparison of the spectral density with the vibrational frequencies is presented.