UC Berkeley

Energy decomposition analysis (EDA) is a useful tool for obtaining chemically meaningful insights into molecular interactions. The extended transition-state method with natural orbitals for chemical valence (ETS-NOCV) and the absolutely localized molecular orbital-based method with complementary occupied-virtual pairs (ALMO-COVP) are two successful EDA schemes. Working within ground-state generalized Kohn-Sham density functional theory (DFT), we extend these methods to perform EDA between any two electronic states that can be connected by a unitary transformation of density matrices. A direct proof that the NOCV eigenvalues are symmetric pairs is given, and we also prove that the charge and energy difference defined by ALMO are invariant under certain orbital rotations, allowing us to define COVPs. We point out that ETS is actually a 1-point quadrature to obtain the effective Fock matrix, and though it is reasonably accurate, it can be systematically further improved by adding more quadrature points. We explain why the calculated amount of transferred charge measured by ALMO-COVP is typically much smaller than that of ETS-NOCV and explain why the ALMO-COVP values should be preferred. While the two schemes are independent, ETS-NOCV and ALMO-COVP in fact give a very similar chemical picture for a variety of chemical interactions, including H-H⁺, the transition structure for the Diels-Alder reaction between ethene and butadiene, and two hydrogen-bonded complexes, H₂O···F^- and H₂O···HF.