Nonadiabatic polaron dynamics from machine-learned hopping trajectories

Abstract

The formation and motion of small polarons are ubiquitous in energy materials and influence photoinduced processes. Polaron transport is governed by thermally activated lattice dynamics and rare hopping events, requiring spatial and temporal scales only attainable with machine-learning molecular dynamics, which enables extensive sampling of atomic trajectories and polaron configurations over nanoseconds. Moreover, the Born-Oppenheimer approximation underlying standard ab initio molecular dynamics cannot describe the nonadiabatic coupling between electronic states mediated by nuclear motion, which controls energy exchange and excited-state relaxation. Here, we develop a simulation framework that combines machine-learning-assisted polaron dynamics with nonadiabatic molecular dynamics to bridge these complementary aspects of polaron physics, and determine how different polaron-hopping mechanisms affect excited-state dynamics. The enlarged trajectory space allows us to provide the first direct dynamical confirmation of the adiabatic or nonadiabatic classification of polaron hopping regimes originally proposed on the basis of static Marcus-theory arguments, and to connect individual hopping events directly to nonadiabatic electronic transitions. In bulk TiO$_2$, nonadiabatic hoppings occur preferentially when the energy of the polaron-induced gap state approaches the conduction-band manifold, promoting both electronic de-excitation and, via a Landau-Zener mechanism, excitation from the ground state. In MgO, the predominantly adiabatic character of hole-polaron hopping suppresses these effects, leading to longer charge-carrier lifetimes and an absence of thermally activated excitations. At the rutile TiO$_2$(110) surface, hopping events are rarer than in bulk because the excess electron is strongly stabilized in the subsurface region, leading to correspondingly longer de-excitation times.