Mean first passage times reconstruct the slowest relaxations in potential energy landscapes of nanoclusters.

Abstract

Relaxation modes are the collective modes in which all probability deviations from equilibrium states decay with the same relaxation rates. In contrast, a first passage time is the required time for arriving for the first time from one state to another. In this paper, we discuss how and why the slowest relaxation rates of relaxation modes are reconstructed from the first passage times. As an illustrative model, we use a continuous-time Markov state model of vacancy diffusion in KCl nanoclusters. Using this model, we reveal that all characteristics of the relaxations in KCl nanoclusters come from the fact that they are hybrids of two kinetically different regions of the fast surface and slow bulk diffusions. The origin of the different diffusivities turns out to come from the heterogeneity of the activation energies on the potential energy landscapes. We also develop a stationary population method to compute the mean first passage times as mean times required for pair annihilations of particle-hole pairs, which enables us to obtain the symmetric results of relaxation rates under the exchange of the sinks and the sources. With this symmetric method, we finally show why the slowest relaxation times can be reconstructed from the mean first passage times.