Breakdown of the ionization potential theorem of density functional theory in mesoscopic systems

Abstract

The IP-theorem of the Kohn-Sham (KS) density functional theory (DFT) states that the energy of the highest occupied molecular orbital (HOMO) ${\epsilon }_{HOMO}$ equals the negative of the first ionization potential (IP), thus ascribing a physical meaning to one of the eigenvalues of the KS hamiltonian. We scrutinize the fact that the validity of the IP-theorem relies critically on the electron density $n(\mathbf{r})$, far from the system, to be determined by HOMO only, behaving as $n(\mathbf{r})\underset{r\to \infty }{\sim }{e}^{-2\sqrt{-2{\epsilon }_{HOMO}}r}$. While this behavior always holds for finite systems, it does not hold for mesoscopic ones, such as quasi-two-dimensional (Q2D) electron gas or Q2D crystals. We show that this leads to the violation of the IP-theorem for the latter class of systems. This finding has a strong bearing on the role of the KS valence band with respect to the work-function problem in the mesoscopic case. Based on our results, we introduce a concept of the IP band structure as an observable alternative to its unphysical KS counterpart. A practical method of the determination of IP band structure in terms of DFT quantities is provided.

8 pages, 4 figures

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