Skip to main content

Research Repository

Advanced Search

System-dependent exchange–correlation functional with exact asymptotic potential and εHOMO ≈ − I

Gledhill, Jonathan D.; Tozer, David J.

System-dependent exchange–correlation functional with exact asymptotic potential and εHOMO ≈ − I Thumbnail


Authors

Jonathan D. Gledhill



Abstract

Density scaling considerations are used to derive an exchange–correlation explicit density functional that is appropriate for the electron deficient side of the integer and which recovers the exact r → ∞ asymptotic behaviour of the exchange–correlation potential. The functional has an unconventional mathematical form with parameters that are system-dependent; the parameters for an N-electron system are determined in advance from generalised gradient approximation (GGA) calculations on the N- and (N − 1)-electron systems. Compared to GGA results, the functional yields similar exchange–correlation energies, but HOMO energies that are an order of magnitude closer to the negative of the vertical ionisation potential; for anions, the HOMO energies are negative, as required. Rydberg excitation energies are also notably improved and the exchange–correlation potential is visibly lowered towards the near-exact potential. Further development is required to improve valence excitations, static isotropic polarisabilities, and the shape of the potential in non-asymptotic regions. The functional is fundamentally different to conventional approximations.

Journal Article Type Article
Acceptance Date Jun 25, 2015
Online Publication Date Jul 9, 2015
Publication Date Jul 14, 2015
Deposit Date Jul 13, 2015
Publicly Available Date Jul 23, 2015
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 143
Issue 2
Article Number 024104
DOI https://doi.org/10.1063/1.4926397
Public URL https://durham-repository.worktribe.com/output/1405247

Files

Published Journal Article (742 Kb)
PDF

Copyright Statement
© 2015 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Journal of Chemical Physics, 143, 024104 (2015) and may be found at http://dx.doi.org/10.1063/1.4926397.






You might also like



Downloadable Citations