Publication details for Prof. David J. TozerSharpe, 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.
- Publication type: Journal Article
- ISSN/ISBN: 1549-9618 (print), 1549-9626 (electronic)
- DOI: 10.1021/acs.jctc.7b01060
- Further publication details on publisher web site
- Durham Research Online (DRO) - may include full text
Author(s) from Durham
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.