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Within a tight-binding approximation, we numerically determine the time evolution of graphene electronic states in the presence of classically vibrating nuclei. There is no reliance on the Born–Oppenheimer approximation within the p-orbital tight-binding basis, although our approximation is “atomically adiabatic”: the basis p-orbitals are taken to follow nuclear positions. Our calculations show that the strict adiabatic Born–Oppenheimer approximation fails badly. We find that a diabatic (lazy electrons responding weakly to nuclear distortions) Born–Oppenheimer model provides a much more accurate picture and suggests a generalized many-body Bloch orbital-nuclear basis set for describing electron–phonon interactions in graphene.
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Hydrogen atom collisions with a semiconductor efficiently promote electrons to the conduction band
Abstract The Born–Oppenheimer approximation is the keystone of modern computational chemistry and there is wide interest in understanding under what conditions it remains valid. Hydrogen atom scattering from insulator, semi-metal and metal surfaces has helped provide such information. The approximation is adequate for insulators and for metals it fails, but not severely. Here we present hydrogen atom scattering from a semiconductor surface: Ge(111) c (2 × 8). Experiments show bimodal energy-loss distributions revealing two channels. Molecular dynamics trajectories within the Born–Oppenheimer approximation reproduce one channel quantitatively. The second channel transfers much more energy and is absent in simulations. It grows with hydrogen atom incidence energy and exhibits an energy-loss onset equal to the Ge surface bandgap. This leads us to conclude that hydrogen atom collisions at the surface of a semiconductor are capable of promoting electrons from the valence to the conduction band with high efficiency. Our current understanding fails to explain these observations.
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- Award ID(s):
- 1951328
- PAR ID:
- 10417777
- Date Published:
- Journal Name:
- Nature Chemistry
- Volume:
- 15
- Issue:
- 3
- ISSN:
- 1755-4330
- Page Range / eLocation ID:
- 326 to 331
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1038/s41557-022-01085-x
