Theoretical study of nonadiabatic hydrogen atom scattering dynamics on metal surfaces using the hierarchical equations of motion method.

Hydrogen atom scattering on metal surfaces is investigated based on a simplified Newns-Anderson model. Both the nuclear and electronic degrees of freedom are treated quantum mechanically. By partitioning all the surface electronic states as the bath, the hierarchical equations of motion method for the fermionic bath is employed to simulate the scattering dynamics. It is found that, with a reasonable set of parameters, the main features of the recent experimental studies of hydrogen atom scattering on metal surfaces can be reproduced. Vibrational states on the chemisorption state whose energies are close to the incident energy are found to play an important role, and the scattering process is dominated by a single-pass electronic transition forth and back between the diabatic physisorption and chemisorption states. Further study on the effects of the atom-surface coupling strength reveals that, upon increasing the atom-surface coupling strength, the scattering mechanism changes from typical nonadiabatic transitions to dynamics in the electronic friction regime.

Probing the Synergistic Effects of Mg2+ on CO2 Reduction Reaction on CoPc by In Situ Electrochemical Scanning Tunneling Microscopy.

We report herein the in situ electrochemical scanning tunneling microscopy (ECSTM) study on the synergistic effect of Mg2+ in CO2 reduction reaction (CO2RR) catalyzed by cobalt phthalocyanine (CoPc). ECSTM measurement molecularly resolves the self-assembled CoPc monolayer on the Au(111) substrate. In the CO2 environment, high-contrast species are observed in the adlayer and assigned to the CO2 adsorption on CoPc. Furthermore, the contrast of the CO2-bound complex is higher in Mg2+-containing electrolytes than in Mg2+-free electrolytes, indicating the formation of the CoPc-CO2-Mg2+ complex. The surface coverage of adsorbed CO2 is positively correlated with the Mg2+ concentration as the additive in electrolytes up to a plateau of 30.8 ± 2.7% when c(Mg2+) > 30 mM. The potential step experiment indicates the higher CO2 adsorption dynamics in Mg2+-containing electrolytes than without Mg2+. The rate constants of CO2 adsorption and dissociation in different electrolytes are extracted from the data fitting of statistical results from in situ ECSTM experiments.

Generalized master equation for charge transport in a molecular junction: Exact memory kernels and their high order expansion.

We derive a set of generalized master equations (GMEs) to study charge transport dynamics in molecular junctions using the Nakajima-Zwanzig-Mori projection operator approach. In the new GME, time derivatives of population on each quantum state of the molecule, as well as the tunneling current, are calculated as the convolution of time non-local memory kernels with populations on all system states. The non-Markovian memory kernels are obtained by combining the hierarchical equations of motion (HEOM) method and a previous derived Dyson relation for the exact kernel. A perturbative expansion of these memory kernels is then calculated using the extended HEOM developed in our previous work [M. Xu et al., J. Chem. Phys. 146, 064102 (2017)]. By using the resonant level model and the Anderson impurity model, we study properties of the exact memory kernels and analyze convergence properties of their perturbative expansions with respect to the system-bath coupling strength and the electron-electron repulsive energy. It is found that exact memory kernels calculated from HEOM exhibit short memory times and decay faster than the population and current dynamics. The high order perturbation expansion of the memory kernels can give converged results in certain parameter regimes. The Padé and Landau-Zener resummation schemes are also found to give improved results over low order perturbation theory.