Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method
Abstract
We introduce an orbital-optimized double-hybrid (DH) scheme using the optimized-effective-potential (OEP) method. The orbitals are optimized using a local potential corresponding to the complete exchange-correlation energy expression including the second-order M{{\o}}ller-Plesset (MP2) correlation contribution. We have implemented a one-parameter version of this OEP-based self-consistent DH scheme using the BLYP density-functional approximation and compared it to the corresponding non-self-consistent DH scheme for calculations on a few closed-shell atoms and molecules. While the OEP-based self-consistency does not provide any improvement for the calculations of ground-state total energies and ionization potentials, it does improve the accuracy of electron affinities and restores the meaning of the LUMO orbital energy as being connected to a neutral excitation energy. Moreover, the OEP-based self-consistent DH scheme provides reasonably accurate exchange-correlation potentials and correlated densities.
Keywords
Cite
@article{arxiv.1607.05481,
title = {Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method},
author = {Szymon Smiga and Odile Franck and Bastien Mussard and Adam Buksztel and Ireneusz Grabowski and Eleonora Luppi and Julien Toulouse},
journal= {arXiv preprint arXiv:1607.05481},
year = {2016}
}
Comments
in The Journal of Chemical Physics, American Institute of Physics, 2016