Orbital Energies and Nuclear Forces in DFT: Interpretation and Validation

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 …