Increasing the applicability of density functional theory. IV. Consequences of ionization-potential improved exchange-correlation potentials
Abstract
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 (VXC). None of the prominently used DFT approaches show these properties: the optimized effective potential VXC based ab initio dftdoes. 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.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Apr 24, 2014
- Source ID
- 10.1063/1.4871409
Entities
People
- Prakash Verma
- Rodney J. Bartlett
Organizations
- Air Force Office of Scientific Research
- University of Florida