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

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.

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Cited by in corpus (7)

• i-PI 3.0: a flexible and efficient framework for advanced atomistic simulations
• Classical quantum friction at water-carbon interfaces
• Semiclassical instanton theory for reaction rates at any temperature: How a rigorous real-time derivation solves the crossover temperature problem
• Electronic Friction Near Metal Surface: Incorporating Nuclear Quantum Effect with Ring Polymer Molecular Dynamics
• Comparison of Matsubara dynamics with exact quantum dynamics for an oscillator coupled to a dissipative bath
• Nonadiabatic transition paths from quantum jump trajectories
• Non-Markovian Effects in Quantum Rate Calculations of Hydrogen Diffusion with Electronic Friction