0521856 - ÚOCHB 2021 RIV DE eng J - Journal Article
Presti, D. - Kadlec, Jan - Truhlar, D. G. - Gagliardi, L.
Scaling exchange and correlation in the on-top density functional of multiconfiguration pair-density functional theory: effect on electronic excitation energies and bond energies.
Theoretical Chemistry Accounts. Roč. 139, č. 2 (2020), č. článku 30. ISSN 1432-881X. E-ISSN 1432-2234
Institutional support: RVO:61388963
Keywords : excitation energies * bond energies * benchmark * MC-PDFT * pair-density * on-top pair-density functionals
OECD category: Physical chemistry
Impact factor: 1.702, year: 2020
Method of publishing: Limited access
Result website:
https://link.springer.com/article/10.1007/s00214-019-2539-6
DOI: https://doi.org/10.1007/s00214-019-2539-6

Multiconfiguration pair-density functional (MC-PDFT) theory provides an economical way to calculate the ground-state and excited-state energetics of strongly correlated systems. The energy is calculated from the kinetic energy, density, and on-top pair-density of a multiconfiguration wave function as the sum of kinetic energy, classical Coulomb energy, and on-top density functional energy. We have usually found good results with the translated Perdew–Burke–Ernzerhof (tPBE) on-top density functional, and in this article, we examine whether the results can be systematically improved by introducing scaling constants into the exchange and correlation terms. We find that only a small improvement is possible for electronic excitation energies and that no improvement is possible for bond energies.

Permanent Link: http://hdl.handle.net/11104/0306408