Orbital energies and nuclear forces in DFT: Interpretation and validation
Author
dc.contributor.author
Laplaza, Rubén
Author
dc.contributor.author
Cárdenas Valencia, Carlos
Author
dc.contributor.author
Chaquin, Patrick
Author
dc.contributor.author
Contreras García, Julia
Author
dc.contributor.author
Ayers, Paul W.
Admission date
dc.date.accessioned
2021-06-15T21:32:21Z
Available date
dc.date.available
2021-06-15T21:32:21Z
Publication date
dc.date.issued
2020
Cita de ítem
dc.identifier.citation
J Comput Chem. 2021;42:334–343
es_ES
Identifier
dc.identifier.other
10.1002/jcc.26459
Identifier
dc.identifier.uri
https://repositorio.uchile.cl/handle/2250/180131
Abstract
dc.description.abstract
The bonding and antibonding character of individual molecular orbitals has been previously
shown to be related to their orbital energy derivatives with respect to nuclear
coordinates, known as dynamical orbital forces. Albeit usually derived from
Koopmans' theorem, in this work we show a more general derivation from conceptual
DFT, which justifies application in a broader context. The consistency of the
approach is validated numerically for valence orbitals in Kohn–Sham DFT. Then, we
illustrate its usefulness by showcasing applications in aromatic and antiaromatic systems
and in excited state chemistry. Overall, dynamical orbital forces can be used to
interpret the results of routine ab initio calculations, be it wavefunction or density
based, in terms of forces and occupations.
es_ES
Patrocinador
dc.description.sponsorship
LabEx MiChem program of Sorbonne Universite
ECOS-Sud action
C17E09
ED388
Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT)
CONICYT FONDECYT
1181121
Centers Of Excellence With Basal/Conicyt Financing
FB0807