Ab initio analysis of proton transfer dynamics in (H2O)3H+

We have harvested ab initio trajectories of proton transfer in (H2O)3H+ by combining Car–Parrinello molecular dynamics (CPMD) with the transition path sampling method. Two transition state regions contribute to these dynamics, with saddle points similar to those identified by Geissler, Dellago, and Chandler for an empirical model of the same cluster [Phys. Chem. Chem. Phys. 1 (1999) 1317]. As in that model, the location of a transition state along a finite-temperature trajectory indicates that proton transfer is driven by reorganization of the oxygen ring. From vibrational properties it is estimated that the characteristic time for proton transfer is ∼1 ns at a temperature of 300 K.