Dissipative Tunneling Rates through the Incorporation of First-Principles Electronic Friction in Instanton Rate Theory II: Benchmarks and Applications

TL;DR

This paper extends a first-principles method for calculating quantum tunneling rates with electronic friction, benchmarking its accuracy and applying it to metal diffusion, revealing the importance of vibrational effects over non-adiabatic effects.

Contribution

It introduces an improved instanton rate theory incorporating electronic friction and demonstrates its effectiveness through benchmarks and realistic metal diffusion applications.

Findings

RPI-EF accurately predicts tunneling rates at medium/high friction

NAEs influence tunneling pathways and cross-over temperature

Vibrational effects dominate over NAEs in metal diffusion rates

Abstract

In part I, we presented the ring-polymer instanton with explicit friction (RPI-EF) method and showed how it can be connected to the \textit{ab initio} electronic friction formalism. This framework allows the calculation of tunneling reaction rates that incorporate the quantum nature of the nuclei and certain types of non-adiabatic effects (NAEs) present in metals. In this second part, we analyze the performance of RPI-EF on model potentials and apply it to realistic systems. For a 1D double-well model, we benchmark the method against numerically exact results obtained from multi-layer multi-configuration time-dependent Hartree calculations. We demonstrate that RPI-EF is accurate for medium and high friction strengths and less accurate for extremely low friction values. We also show quantitatively how the inclusion of NAEs lowers the cross-over temperature into the deep tunneling regime, reduces the tunneling rates, and in certain regimes, steers the quantum dynamics by modifying the tunneling pathways. As a showcase of the efficiency of this method, we present a study of hydrogen and deuterium hopping between neighboring interstitial sites in selected bulk metals. The results show that multidimensional vibrational coupling and nuclear quantum effects have a larger impact than NAEs on the tunneling rates of diffusion in metals. Together with part I, these results advance the calculations of dissipative tunneling rates from first principles.