Transition pathway of hydrogen bond switching in supercooled water analyzed by the Markov state model

In this work, we examine hydrogen-bond (H-bond) switching by employing the Markov State Model (MSM). During the H-bond switching, a water hydrogen initially H-bonded with water oxygen becomes H-bonded to a different water oxygen. MSM analysis was applied to trajectories generated from molecular dynamics simulations of the TIP4P/2005 model from a room-temperature state to a supercooled state. We defined four basis states to characterize the configuration between two water molecules: H-bonded ("H"), unbound ("U"), weakly H-bonded ("w"), and alternative H-bonded ("a") states. A 16 × 16 MSM matrix was constructed, describing the transition probability between states composed of three water molecules. The mean first-passage time of the H-bond switching was estimated by calculating the total flux from the HU to UH states. It is demonstrated that the temperature dependence of the mean first-passage time is in accordance with that of the H-bond lifetime determined from the H-bond correlation function. Furthermore, the flux for the H-bond switching is decomposed into individual pathways that are characterized by different forms of H-bond configurations of trimers. The dominant pathway of the H-bond switching is found to be a direct one without passing through such intermediate states as "w" and "a," the existence of which becomes evident in supercooled water. The pathway through "w" indicates a large reorientation of the donor molecule. In contrast, the pathway through "a" utilizes the tetrahedral H-bond network, which is revealed by the further decomposition based on the H-bond number of the acceptor molecule.