Orbital energies and nuclear forces in DFT: Interpretation and validation
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2020Metadata
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Laplaza, Rubén
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Orbital energies and nuclear forces in DFT: Interpretation and validation
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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.
Patrocinador
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
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J Comput Chem. 2021;42:334–343
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