Improved Projection-Operator Diabatization Schemes for the Calculation of Electronic Coupling Values

We address a long-standing ambiguity in the DFT-based projection-operator diabatization method for charge transfer couplings in donor-acceptor systems. It has long been known that the original method yields diabats which are not strictly fragment-localized due to mixing arising from basis-set orthogonalization. We demonstrate that this can contribute to a severe underestimation of coupling strengths and a spurious dependence on the choice of the basis set. As a remedy, we reformulate the method within a simple tight-binding model to generate diabats with increased localization, yielding a proper basis set convergence and improved performance for the general Hab11 benchmark set. Orthogonality of diabats is ensured either through symmetric Löwdin or asymmetric Gram-Schmid procedures, the latter of which offers to extend these improvements to asymmetric systems such as adsorbates on surfaces.