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Orbital Energies and Nuclear Forces in DFT: Interpretation and Validation

preprint
submitted on 19.06.2020, 18:42 and posted on 24.06.2020, 13:06 by Rubén Laplaza, Julia Contreras-Garcia, Patrick Chaquin, Carlos Cardenas, Paul W. Ayers
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.

History

Email Address of Submitting Author

rlaplaza@lct.jussieu.fr

Institution

Laboratoire de Chimie Théorique

Country

France

ORCID For Submitting Author

https://orcid.org/0000-0001-6315-4398

Declaration of Conflict of Interest

No conflict of interest to declare.

Version Notes

This is the first version, and may be updated in the future.

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