skip to main content

SciTech ConnectSciTech Connect

Title: Increasing the applicability of density functional theory. IV. Consequences of ionization-potential improved exchange-correlation potentials

This paper's objective is to create a “consistent” mean-field based Kohn-Sham (KS) density functional theory (DFT) meaning the functional should not only provide good total energy properties, but also the corresponding KS eigenvalues should be accurate approximations to the vertical ionization potentials (VIPs) of the molecule, as the latter condition attests to the viability of the exchange-correlation potential (V{sub XC}). None of the prominently used DFT approaches show these properties: the optimized effective potential V{sub XC} based ab initio dft does. A local, range-separated hybrid potential cam-QTP-00 is introduced as the basis for a “consistent” KS DFT approach. The computed VIPs as the negative of KS eigenvalue have a mean absolute error of 0.8 eV for an extensive set of molecule's electron ionizations, including the core. Barrier heights, equilibrium geometries, and magnetic properties obtained from the potential are in good agreement with experiment. A similar accuracy with less computational efforts can be achieved by using a non-variational global hybrid variant of the QTP-00 approach.
Authors:
;  [1]
  1. Quantum Theory Project, University of Florida, Gainesville, Florida 32611 (United States)
Publication Date:
OSTI Identifier:
22253049
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 18; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; APPROXIMATIONS; DENSITY FUNCTIONAL METHOD; EIGENVALUES; IONIZATION; MAGNETIC PROPERTIES; MEAN-FIELD THEORY; POTENTIALS