Regensburg 2019 – wissenschaftliches Programm

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O: Fachverband Oberflächenphysik

O 11: Frontiers of Electronic-Structure Theory: Focus on the Interface Challenge II (joint session O/CPP/DS/TT)

O 11.8: Vortrag

Montag, 1. April 2019, 16:45–17:00, H9

Ab-initio description of transient ion formation of NO on Au(111) — Daniel Corken, Nicholas D. M. Hine, and •Reinhard J. Maurer — Departments of Physics and Chemistry, University of Warwick, United Kingdom

Gaining a fundamental understanding of the interactions of molecules on metal surfaces is essential for the development of novel heterogeneous catalysts. An interesting feature of gas-surface reactions at metal surfaces is that the Born-Oppenheimer approximation breaks down. Vibrationally excited and translationally hot molecules can transfer energy to the electrons of a metal via excitation of electron-hole pairs (EHP). In case of NO on Au(111), [1] this nonadiabatic energy loss is believed to stem from the transient generation of charged ion species at the surface. A computationally feasible and accurate description of such a molecule-metal charge-transfer state represents a challenge and several methods have been proposed. Upon a review of existing experimental evidence, we will present our approach to this problem. We use linear expansion-Delta-Self-Consistent-Field Density Functional Theory (leΔSCF-DFT) [2] to model the anionic resonance of NO on Au(111). The leΔSCF-DFT method enforces the electronic configuration of reference molecular states while solving the Kohn-Sham equations self-consistently. By comparison to experiment and other models, we asses the methods’ ability to describe the ground- and excited-states during molecular scattering. We further explore avenues to extract nonadiabatic couplings and to construct model Hamiltonians based on this method. [1] JCP 130, 174716, [2] JCP 139, 014708;