Nuclear Quantum Effects on Proton Diffusivity in Perovskite Oxides

TL;DR

This study investigates how nuclear quantum effects influence proton movement in perovskite oxides, revealing that classical models overestimate activation energies and that quantum effects are crucial for accurate diffusivity predictions.

Contribution

The paper demonstrates the importance of including nuclear quantum effects in simulations of proton diffusivity, challenging the adequacy of classical transition state theory for such systems.

Findings

Classical TST overestimates activation energy for proton hopping.

Nuclear quantum effects cause nonlinear temperature dependence of jump frequencies.

Quantum effects are significant in the 500-2000 K temperature range.

Abstract

In the present study, the nuclear quantum effects (NQEs) on proton diffusivity in oxides were evaluated by molecular dynamics (MD) simulations with the quantum thermal bath (QTB) based on the Langevin dynamics. We employed the proton diffusion in barium zirconate (BaZrO3) with the cubic perovskite structure as the model system, in which protons migrate by rotation around single oxide ions and hopping between adjacent oxide ions. MD simulations with the standard classical thermal bath (CTB) and phonon calculations were also conducted to verify the conventionally used classical harmonic transition state theory (classical h-TST), in which the transition state theory (TST), the harmonic approximation, and the classical approximation are assumed. As a result, the h-TST are reasonable for the proton rotation, while significantly overestimate the activation energy and the pre-exponential factor of the jump frequency for the proton hopping. Furthermore, the classical approximation makes the proton jump frequencies close to linear in the Arrhenius plots, which should actually be nonlinear by the NQEs in the temperature range of 500-2000 K. This suggests the necessity of the treatment beyond the classical h-TST for accurate evaluation of the proton diffusivity in oxides even in the intermediate temperature range (573-873 K).