This work explores the electronic structure as well as the reactivity of singlet diradicals, making use of multistate density functional theory (MSDFT). In particular, we show that a minimal active space of two electrons in two orbitals is adequate to treat the relative energies of the singlet and triplet adiabatic ground state as well as the first singlet excited state in many cases. This is plausible because dynamic correlation is included in the first place in the optimization of orbitals in each determinant state via block-localized Kohn–Sham density functional theory. In addition, molecular fragment, i.e., block-localized Kohn–Sham orbitals, are optimized separately for each determinant, providing a variational diabatic representation of valence bond-like states, which are subsequently used in nonorthogonal state interactions (NOSIs). The computational procedure and its performance are illustrated on some prototypical diradical species. It is shown that NOSI calculations in MSDFT can be used to model bond dissociation and hydrogen-atom transfer reactions, employing a minimal number of configuration state functions as the basis states. For p- and s-types of diradicals, the closed-shell diradicals are found to be more reactive than the open-shell ones due to a larger diabatic coupling with the final product state. Such a diabatic representation may be useful to define reaction coordinates for electron transfer, proton transfer and coupled electron and proton transfer reactions in condensed-phase simulations.

Variational energy decomposition analyses have been presented to quantify the σ-dative, ligand-to-metal forward charge transfer (CT) and the π-conjugative, metal-to-ligand backward charge delocalization on a series of isolelectronic transition-metal carbonyl complexes M­(CO)6, including M = Ti2–, V–, Cr, Mn+, and Fe2+. Although the qualitative features of these energy terms are understood, well-defined quantitative studies have been scarce. Consistent with early findings, electrostatic and Pauli exchange effects play a key role in σ-donation, resulting in blue shifts in ligand vibrational frequency in the complex geometries. Excluding chemical bonding interactions between the CO ligand and the metal fragments in the energy decomposition analysis, we found that loosely bound electrostatic complexes can be formed at a longer metal-to-ligand distance due to the exponential decay of Pauli exchange. In all complexes, the overall binding stabilization can be attributed to CT effects, with opposing trends between σ-donation and π-back bonding that follows an order of Ti2– (4.4) > V1– (2.6) > Cr (1.5) > Mn1+ (1.1) > Fe2+ (0.5) in π-to-σ CT ratio. These electronic and energetic features are mirrored in the vibrational frequency shifts induced by different factors. The present investigation may help stimulate the use of energy decomposition techniques to understand the structure and activity of metallocatalysts using density functional theory.