Estimating local bonding/antibonding character of canonical molecular orbitals from their energy derivatives. The case of coordinating lone pair orbitals

According to Koopmans theorem, the derivative of the energy of a canonical molecular orbital (MO) with respect to nuclear coordinates quantifies its bonding/antibonding character. This quantity allows predictions of bond length variation on ionisation in a panel of 19 diatomic species. In polyatomic molecules, the derivative of a MO energy with respect to a given bond length reveals the nature and the degree of the bonding/antibonding contribution of this MO with respect to this bond. Accordingly, the HOMO “lone pairs” of CO and CN− and the HOMO‐2 of CH3CN are found to be antibonding with respect to the CX bond (X = N, O), whereas the HOMO of N2 is found to be bonding. With the same approach, the variation of the bonding character in the MOs of CO and CH3CN on interaction with an electron acceptor (modeled through the approach of a proton) or by applying an electric field was studied. © 2016 Wiley Periodicals, Inc. Molecular orbital energy derivatives with respect to a given bond length provides a simple criterion of bonding/antibonding character of the orbital with respect to this bond in diatomic and polyatomic molecules. For example, the HOMO lone pair of CO and the HOMO‐2 one of CH3CN are found antibonding, whereas the HOMO of N2 is found bonding. This method appears as a useful tool to rationalize the effects of donor–acceptor interactions.