First-Principles Nonadiabatic Dynamics via the Multi-Orbital Anderson-Newns Model
Abstract
We develop a first-principles theory for nonadiabatic surface dynamics, providing a fit-free connection between density functional theory (DFT) calculations and the effective multi-orbital Anderson-Newns (AN) theory. Our theory contains two main advances. First, we outline the multi-orbital AN theory with orbital overlap and derive closed-form expressions for the hybridization energy, electronic dynamics, and electronic friction. Second, we describe a procedure to map the DFT Hamiltonian into the effective AN Hamiltonian with nuclear-position dependence. We obtain the electronic part of the AN Hamiltonian solely from the adsorbate-projected density-of-states matrix. We then define the bare nuclear potential as the difference between the total energy and the hybridization energy. The theory is applied to H and CO on the Cu surface, where widely used assumptions about the hybridization function, including the wide-band limit, semi-elliptical forms, and separability in energy and nuclear coordinate, are found to fail, and the single-orbital description breaks down qualitatively for CO. We expect this work to be broadly useful for first-principles modeling of coupled nuclear-electronic dynamics and chemical reactions at metallic surfaces.
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BibTeX
@misc{ko2026firstprinciples,
title = {{First-Principles Nonadiabatic Dynamics via the Multi-Orbital Anderson-Newns Model}},
author = {Liwen Ko and Joonho Lee},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.27000},
eprint = {2609.27000},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.27000},
}
RIS
TY - UNPB
TI - First-Principles Nonadiabatic Dynamics via the Multi-Orbital Anderson-Newns Model
AU - Liwen Ko
AU - Joonho Lee
PY - 2026
DA - 2026/09/29
PB - arXiv
DO - 10.48550/arxiv.2609.27000
UR - https://arxiv.org/abs/2609.27000
AB - We develop a first-principles theory for nonadiabatic surface dynamics, providing a fit-free connection between density functional theory (DFT) calculations and the effective multi-orbital Anderson-Newns (AN) theory. Our theory contains two main advances. First, we outline the multi-orbital AN theory with orbital overlap and derive closed-form expressions for the hybridization energy, electronic dynamics, and electronic friction. Second, we describe a procedure to map the DFT Hamiltonian into the effective AN Hamiltonian with nuclear-position dependence. We obtain the electronic part of the AN Hamiltonian solely from the adsorbate-projected density-of-states matrix. We then define the bare nuclear potential as the difference between the total energy and the hybridization energy. The theory is applied to H and CO on the Cu surface, where widely used assumptions about the hybridization function, including the wide-band limit, semi-elliptical forms, and separability in energy and nuclear coordinate, are found to fail, and the single-orbital description breaks down qualitatively for CO. We expect this work to be broadly useful for first-principles modeling of coupled nuclear-electronic dynamics and chemical reactions at metallic surfaces.
ER -