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arXiv · 1607.05481

Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method

Szymon Smiga·Odile Franck·Bastien Mussard·Adam Buksztel·Ireneusz Grabowski·Eleonora Luppi·Julien Toulouse
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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{ø}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.

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Szymon Smiga, Odile Franck, Bastien Mussard, Adam Buksztel, Ireneusz Grabowski, Eleonora Luppi, Julien Toulouse. 2016-09-23. Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method. https://doi.org/10.1063/1.4964319

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