Real-Time Coupled Electron-Nuclear Dynamics of Chemical Bond Formation: Hydrogen Scattering from a Semiconductor Surface

Fuente: arXiv
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Main Authors: Shi, Jialong, Zhu, Lingjun, Nitz, Florian, Bünermann, Oliver, Wodtke, Alec M., Guo, Hua, Jiang, Bin
Format: Preprint
Published: 2025
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author Shi, Jialong
Zhu, Lingjun
Nitz, Florian
Bünermann, Oliver
Wodtke, Alec M.
Guo, Hua
Jiang, Bin
author_facet Shi, Jialong
Zhu, Lingjun
Nitz, Florian
Bünermann, Oliver
Wodtke, Alec M.
Guo, Hua
Jiang, Bin
contents A first-principles coupled electron-nuclear dynamics simulation based on real-time, time-dependent density functional theory and Ehrenfest dynamics quantitatively repro-duces bimodal translational energy loss and angular distributions observed in experiment for hydrogen atom scattering from Ge(111)-c(2*8). The theory elucidates a site-selective mechanism of electronically nonadiabatic energy transfer associated with the formation of different Ge-H bonds. When a hydrogen atom approaches a Ge rest-atom, it is strongly accelerated toward the potential minimum forming a transient Ge-H bond and then re-flected by the repulsive wall. This transient bond formation triggers an ultrafast electron transfer event from the rest-atom to an adjacent Ge-adatom, involving several crossings between valence and conduction bands of the substrate. Electronic equilibration is impos-sible within such a short time (Born-Oppenheimer failure) allowing the H-atom kinetic energy to be converted to inter-band electronic excitation of the substrate. H-atom colli-sions at other Ge atoms also form a transient bond but exhibit no electronic excitation, resulting in distinctly less efficient energy loss in scattered H-atoms. The nucle-ar-to-electronic energy transfer observed in this system reflects the electronic dynamics of covalent bond formation at a semiconductor surface, a mechanism that is quite distinct from previously identified nonadiabatic energy transfer mechanisms at metal surfaces mediated by electronic friction or transient negative ions.
format Preprint
id arxiv_https___arxiv_org_abs_2512_03753
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Real-Time Coupled Electron-Nuclear Dynamics of Chemical Bond Formation: Hydrogen Scattering from a Semiconductor Surface
Shi, Jialong
Zhu, Lingjun
Nitz, Florian
Bünermann, Oliver
Wodtke, Alec M.
Guo, Hua
Jiang, Bin
Chemical Physics
Materials Science
A first-principles coupled electron-nuclear dynamics simulation based on real-time, time-dependent density functional theory and Ehrenfest dynamics quantitatively repro-duces bimodal translational energy loss and angular distributions observed in experiment for hydrogen atom scattering from Ge(111)-c(2*8). The theory elucidates a site-selective mechanism of electronically nonadiabatic energy transfer associated with the formation of different Ge-H bonds. When a hydrogen atom approaches a Ge rest-atom, it is strongly accelerated toward the potential minimum forming a transient Ge-H bond and then re-flected by the repulsive wall. This transient bond formation triggers an ultrafast electron transfer event from the rest-atom to an adjacent Ge-adatom, involving several crossings between valence and conduction bands of the substrate. Electronic equilibration is impos-sible within such a short time (Born-Oppenheimer failure) allowing the H-atom kinetic energy to be converted to inter-band electronic excitation of the substrate. H-atom colli-sions at other Ge atoms also form a transient bond but exhibit no electronic excitation, resulting in distinctly less efficient energy loss in scattered H-atoms. The nucle-ar-to-electronic energy transfer observed in this system reflects the electronic dynamics of covalent bond formation at a semiconductor surface, a mechanism that is quite distinct from previously identified nonadiabatic energy transfer mechanisms at metal surfaces mediated by electronic friction or transient negative ions.
title Real-Time Coupled Electron-Nuclear Dynamics of Chemical Bond Formation: Hydrogen Scattering from a Semiconductor Surface
topic Chemical Physics
Materials Science
url https://arxiv.org/abs/2512.03753