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Landscape of an exact energy functional

Accepted version
Peer-reviewed

Repository DOI


Type

Article

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Authors

Cohen, Aron J 
Mori-Sanchez, Paula 

Abstract

One of the great challenges of electronic structure theory is the quest for the exact functional of density functional theory. Its existence is proven, but it is a complicated multivariable functional that is almost impossible to conceptualize. In this paper the asymmetric two-site Hubbard model is studied, which has a two-dimensional universe of density matrices. The exact functional becomes a simple function of two variables whose threedimensional energy landscape can be visualized and explored. A walk on this unique landscape, tilted to an angle defined by the one-electron Hamiltonian, gives a valley whose minimum is the exact total energy. This is contrasted with the landscape of some approximate functionals, explaining their failure for electron transfer in the strongly correlated limit. We show concrete examples of pure-state density matrices that are not v representable due to the underlying nonconvex nature of the energy landscape. The exact functional is calculated for all numbers of electrons, including fractional, allowing the derivative discontinuity to be visualized and understood. The fundamental gap for all possible systems is obtained solely from the derivatives of the exact functional.

Description

Keywords

49 Mathematical Sciences, 34 Chemical Sciences, 3407 Theoretical and Computational Chemistry, 7 Affordable and Clean Energy

Journal Title

PHYSICAL REVIEW A

Conference Name

Journal ISSN

2469-9926
2469-9934

Volume Title

93

Publisher

American Physical Society (APS)
Sponsorship
We gratefully acknowledge funding from Ramon y Cajal (P.M.-S.) and the Royal Society (A.J.C.). P.M.S. also acknowledges funding from MINECO Grant No. FIS2015-64886-C5-5-P.