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Auteurs principaux: Bernhard, Théophane, Grisafi, Andrea
Format: Preprint
Publié: 2026
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Accès en ligne:https://arxiv.org/abs/2601.05660
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author Bernhard, Théophane
Grisafi, Andrea
author_facet Bernhard, Théophane
Grisafi, Andrea
contents The response of the Fermi energy to external perturbations governs key physical observables at metallic interfaces. Although this response admits a local formulation in terms of the Fukui function, its evaluation has traditionally been limited by inherent approximations, fundamentally rooted in the difficulty of adding a finite charge in a periodic system. We present an exact resolution to this problem that leverages the screening properties of electronic conductors to compute Fukui functions via a finite electric field. The resulting linear-response theory yields strictly quadratic error scaling of Fermi-level shifts across representative platinum surfaces, achieving sub-meV accuracy up to fields of 0.1 V/Å. The approach is further validated by reproducing work-function changes under molecular perturbations, and by providing mean-field estimates of electrode potentials that yield capacitance--voltage curves consistent with experiment. Our findings establish a rigorous foundation for a local theory relating electrostatic screening and Fermi-energy variations at metallic interfaces.
format Preprint
id arxiv_https___arxiv_org_abs_2601_05660
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Exact Theory of Fermi-Energy Response at Metallic Interfaces
Bernhard, Théophane
Grisafi, Andrea
Materials Science
The response of the Fermi energy to external perturbations governs key physical observables at metallic interfaces. Although this response admits a local formulation in terms of the Fukui function, its evaluation has traditionally been limited by inherent approximations, fundamentally rooted in the difficulty of adding a finite charge in a periodic system. We present an exact resolution to this problem that leverages the screening properties of electronic conductors to compute Fukui functions via a finite electric field. The resulting linear-response theory yields strictly quadratic error scaling of Fermi-level shifts across representative platinum surfaces, achieving sub-meV accuracy up to fields of 0.1 V/Å. The approach is further validated by reproducing work-function changes under molecular perturbations, and by providing mean-field estimates of electrode potentials that yield capacitance--voltage curves consistent with experiment. Our findings establish a rigorous foundation for a local theory relating electrostatic screening and Fermi-energy variations at metallic interfaces.
title Exact Theory of Fermi-Energy Response at Metallic Interfaces
topic Materials Science
url https://arxiv.org/abs/2601.05660