Position-dependent exact-exchange energy for slabs and semi-infinite jellium

TL;DR

This paper investigates the position-dependent exact-exchange energy per particle at metal surfaces using jellium models, revealing asymptotic behaviors and differences between slabs and semi-infinite jellium, with implications for density functional theory.

Contribution

It provides analytical and numerical analysis of the asymptotic behavior of the exchange energy in jellium models, highlighting differences between slabs and semi-infinite systems and their relation to the exchange potential.

Findings

In vacuum, the exchange energy per particle approaches -e^2/2z for slabs.

The asymptotic behavior of semi-infinite jellium differs, with a density-dependent coefficient.

In the low-density limit, slab and semi-infinite jellium exchange energies coincide with a universal coefficient.

Abstract

The position-dependent exact-exchange energy per particle $\varepsilon_x(z)$ (defined as the interaction between a given electron at $z$ and its exact-exchange hole) at metal surfaces is investigated, by using either jellium slabs or the semi-infinite (SI) jellium model. For jellium slabs, we prove analytically and numerically that in the vacuum region far away from the surface $\varepsilon_{x}^{\text{Slab}}(z \to \infty) \to - e^{2}/2z$, {\it independent} of the bulk electron density, which is exactly half the corresponding exact-exchange potential $V_{x}(z \to \infty) \to - e^2/z$ [Phys. Rev. Lett. {\bf 97}, 026802 (2006)] of density-functional theory, as occurs in the case of finite systems. The fitting of $\varepsilon_{x}^{\text{Slab}}(z)$ to a physically motivated image-like expression is feasible, but the resulting location of the image plane shows strong finite-size oscillations every time a slab discrete energy level becomes occupied. For a semi-infinite jellium, the asymptotic behavior of $\varepsilon_{x}^{\text{SI}}(z)$ is somehow different. As in the case of jellium slabs $\varepsilon_{x}^{\text{SI}}(z \to \infty)$ has an image-like behavior of the form $\propto - e^2/z$, but now with a density-dependent coefficient that in general differs from the slab universal coefficient 1/2. Our numerical estimates for this coefficient agree with two previous analytical estimates for the same. For an arbitrary finite thickness of a jellium slab, we find that the asymptotic limits of $\varepsilon_{x}^{\text{Slab}}(z)$ and $\varepsilon_{x}^{\text{SI}}(z)$ only coincide in the low-density limit ($r_s \to \infty$), where the density-dependent coefficient of the semi-infinite jellium approaches the slab {\it universal} coefficient 1/2.