Nonadiabatic effects that arise from the concerted motion of electrons and atoms at comparable energy and time scales are omnipresent in thermal and light-driven chemistry at metal surfaces. Excited (hot) electrons can measurably affect molecule–metal reactions by contributing to state-dependent reaction probabilities. Vibrational state-to-state scattering of NO on Au(111) has been one of the most studied examples in this regard, providing a testing ground for developing various nonadiabatic theories. This system is often cited as the prime example for the failure of electronic friction theory, a very efficient model accounting for dissipative forces on metal-adsorbed molecules due to the creation of hot electrons in the metal. However, the exact failings compared to experiment and their origin from theory are not established for any system because dynamic properties are affected by many compounding simulation errors of which the quality of nonadiabatic treatment is just one. We use a high-dimensional machine learning representation of electronic structure theory to minimize errors that arise from quantum chemistry. This allows us to perform a comprehensive quantitative analysis of the performance of nonadiabatic molecular dynamics in describing vibrational state-to-state scattering of NO on Au(111) and compare directly to adiabatic results. We find that electronic friction theory accurately predicts elastic and single-quantum energy loss but underestimates multiquantum energy loss and overestimates molecular trapping at high vibrational excitation. Our analysis reveals that multiquantum energy loss can potentially be remedied within friction theory whereas the overestimation of trapping constitutes a genuine breakdown of electronic friction theory. Addressing this overestimation for dynamic processes in catalysis and surface chemistry will likely require more sophisticated theories

Molecular motion at metallic surfaces is affected by nonadiabatic effects and electron-phonon coupling. The ensuing energy dissipation and dynamical steering effects are not captured by classical molecular dynamics simulations, but can be described with the molecular dynamics with electronic friction method and linear response calculations based on density functional theory. Herein, we present an implementation of electron-phonon response based on an all-electron numeric atomic orbital description in the electronic structure code FHI-aims. After providing details of the underlying approximations and numerical considerations, we present significant scalability and performance improvements of the new code compared to a previous implementation (Maurer et al 2016 Phys. Rev. B 94 115432). We compare convergence behaviour and results of our simulations for exemplary systems such as H₂ adsorption on Cu(111), and CO on Ru(0001) against existing plane wave implementations. We examine different expressions to calculate electronic friction and vibrational lifetimes for their reliability and ease of convergence. Finally, we show the capabilities of the new code by studying the contribution of interband and intraband excitations to the vibrational lifetime of aperiodic adsorbate motion in large, previously unfeasible, periodic surface models.

The optical and catalytic properties of magnesium nanoclusters are characterized in the context of plasmonic catalysis. Ab initio simulations reveal the propensity for plasmonic enhancement of hydrogen dissociation and evolution.

Orientation dependent energy transfer in NO(v = 3) scattered from Au(111) reproduced by theory for the first time.

In Paper I [Litman et al., J. Chem. Phys. (in press) (2022)], we presented the ring-polymer instanton with explicit friction (RPI-EF) method and showed how it can be connected to the ab initio electronic friction formalism. This framework allows for 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 paper, 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 crossover 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 Paper I [Litman et al., J. Chem. Phys. (in press) (2022)], these results advance the calculations of dissipative tunneling rates from first principles.

Reactions involving adsorbates on metallic surfaces and impurities in bulk metals are ubiquitous in a wide range of technological applications. The theoretical modeling of such reactions presents a formidable challenge for theory because nuclear quantum effects (NQEs) can play a prominent role and the coupling of the atomic motion with the electrons in the metal gives rise to important non-adiabatic effects (NAEs) that alter atomic dynamics. In this work, we derive a theoretical framework that captures both NQEs and NAEs and, due to its high efficiency, can be applied to first-principles calculations of reaction rates in high-dimensional realistic systems. More specifically, we develop a method that we coin ring polymer instanton with explicit friction (RPI-EF), starting from the ring polymer instanton formalism applied to a system–bath model. We derive general equations that incorporate the spatial and frequency dependence of the friction tensor and then combine this method with the ab initio electronic friction formalism for the calculation of thermal reaction rates. We show that the connection between RPI-EF and the form of the electronic friction tensor presented in this work does not require any further approximations, and it is expected to be valid as long as the approximations of both underlying theories remain valid.