Non-empirical exchange-correlation parameterizations based on exact conditions from correlated orbital theory

Autor(es)

Haiduke, Roberto Luiz A. ^{[1, 2]} ; Bartlett, Rodney J. ^[2]

Afiliação do(s) autor(es)

^[1] Univ Sao Paulo, Sao Carlos Inst Chem, CP 780, BR-13560970 Sao Carlos, SP - Brazil

^[2] Univ Florida, Quantum Theory Project, Gainesville, FL 32611 - USA

• Tipo de documento: Artigo Científico
• Fonte: Journal of Chemical Physics; v. 148, n. 18 MAY 14 2018.
• Citações Web of Science: 6

Resumo

Some of the exact conditions provided by the correlated orbital theory are employed to propose new non-empirical parameterizations for exchange-correlation functionals from Density Functional Theory (DFT). This reparameterization process is based on range-separated functionals with 100% exact exchange for long-range interelectronic interactions. The functionals developed here, CAM-QTP-02 and LC-QTP, show mitigated self-interaction error, correctly predict vertical ionization potentials as the negative of eigenvalues for occupied orbitals, and provide nice excitation energies, even for challenging charge-transfer excited states. Moreover, some improvements are observed for reaction barrier heights with respect to the other functionals belonging to the quantum theory project (QTP) family. Finally, the most important achievement of these new functionals is an excellent description of vertical electron affinities (EAs) of atoms and molecules as the negative of appropriate virtual orbital eigenvalues. In this case, the mean absolute deviations for EAs in molecules are smaller than 0.10 eV, showing that physical interpretation can indeed be ascribed to some unoccupied orbitals from DFT. Published by AIP Publishing. (AU)

• Processo FAPESP: 16/18704-2 - Reparametrização de funcionais de troca - correlação baseada no teorema de potenciais de ionização de Bartlett
• Beneficiário: Roberto Luiz Andrade Haiduke
• Modalidade de apoio: Bolsas no Exterior - Pesquisa