We recently extended our energy decomposition analysis based on absolutely localized orbitals (ALMO-EDA) in two aspects: First, we defined a variational forward–backward (VFB) approach to decompose the overall charge transfer (CT) stabilization energy into contributions from forward and backward donation. Such a decomposition is achieved by introducing two additional constrained intermediate states in which only one direction of CT is permitted. These two “one-way” CT states are variationally relaxed such that the associated nuclear forces can be readily obtained. This allows for a facile integration into the previously developed adiabatic EDA scheme, so that the molecular property changes arising from forward and back donation can be separately assigned. Second, we developed an ALMO-EDA scheme that allows to include continuum solvation models. In this scheme, all the intermediate states involved in the variational EDA procedure are computed with the presence of a solvent environment so that solvation effects are incorporated in the evaluation of all its energy components. These extensions allow us to study the energetic, geometric, and vibrational features of π acidic ligands such as CO or N2 to main group and transition metal moieties such as BeO or [Ru(II)(NH3)5]2+. Furthermore, we study the influence of charged substituents on molecular CO2 reduction catalysts. These fundamental insights can be valuable input for the rational design of N2 and CO2 reduction catalysts.

Metal-ligand bonding: A novel perspective based on an extended ALMO-EDA formalism

ACS Spring Meeting 2021

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