Cookies

We use cookies to ensure that we give you the best experience on our website. You can change your cookie settings at any time. Otherwise, we'll assume you're OK to continue.

Durham University

Research & business

View Profile

Publication details for Prof. David J. Tozer

Sharpe, Daniel J., Levy, Mel & Tozer, David J. (2018). Approximating the Shifted Hartree-Exchange-Correlation Potential in Direct Energy Kohn–Sham Theory. Journal of Chemical Theory and Computation 14(2): 684–692.

Author(s) from Durham

Abstract

Levy and Zahariev [Phys. Rev. Lett. 113 113002 (2014)] have proposed a new approach for performing density functional theory calculations, termed direct energy Kohn–Sham (DEKS) theory. In this approach, the electronic energy equals the sum of orbital energies, obtained from Kohn–Sham-like orbital equations involving a shifted Hartree-exchange-correlation potential, which must be approximated. In the present study, density scaling homogeneity considerations are used to facilitate DEKS calculations on a series of atoms and molecules, leading to three nonlocal approximations to the shifted potential. The first two rely on preliminary Kohn–Sham calculations using a standard generalized gradient approximation (GGA) exchange-correlation functional and the results illustrate the benefit of describing the dominant Hartree component of the shift exactly. A uniform electron gas analysis is used to eliminate the need for these preliminary Kohn–Sham calculations, leading to a potential with an unconventional form that yields encouraging results, providing strong motivation for further research in DEKS theory.