Abstract

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. Short-lived excited (hot) electrons can measurably affect molecule-metal reactions by introducing energy dissipation, dynamical steering effects, and by contributing to state-dependent reaction probabilities. [1] Recent experiments have revealed that hot electrons, created by plasmonic decay upon light exposure, can selectively activate chemical reactions at metal catalyst surfaces. I will present our recent efforts to establish a molecular dynamics method that incorporates important nonadiabatic and quantum effects that arise from hot electrons at metal surfaces. We employ a system-bath description of hot electron effects via the molecular dynamics with electronic friction method (MDEF). By combining linear response calculations based on Density Functional Theory [2] with high-dimensional machine-learning-based representations, [3] we are able to apply this approach in comprehensive quantitative simulations for important reference problems, such as the vibrational state-to-state scattering of NO on Au(111). [4] In doing so, we can identify the regimes in which MDEF is valid. I further provide a detailed analysis of the limitations of the existing approach and our ongoing efforts to include quantum tunnelling effects, memory effects, and explicit excited-state effects to capture the dynamics of light-driven hot-electron chemistry. [1] Bartels et al, Chem. Sci. 2, 1647−1655 (2011) [2] R. J. Maurer, M. Askerka, V. S. Batista, J. C. Tully, Phys. Rev. B 94 , 115432 (2016) [3] Y. Zhang, R. J. Maurer, B. Jiang, J. Phys. Chem. C 124 , 186-195 (2020) [4] C. L. Box, Y. Zhang, R. Yin, B. Jiang, R. J. Mauer, JACS Au, DOI : 10.1021/jacsau.0c00066 (2020)