Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method - Sorbonne Université
Article Dans Une Revue The Journal of Chemical Physics Année : 2016

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

Résumé

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 Møller-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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Dates et versions

hal-01346158 , version 1 (18-07-2016)
hal-01346158 , version 2 (23-09-2016)

Identifiants

Citer

Szymon Smiga, Odile Franck, Bastien Mussard, Adam Buksztel, Ireneusz Grabowski, et al.. Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method. The Journal of Chemical Physics, 2016, 145, pp.144102. ⟨10.1063/1.4964319⟩. ⟨hal-01346158v2⟩
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