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

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Reuter,  Karsten
Chair for Theoretical Chemistry and Catalysis Research Center, Technical University of Munich;
Theory, Fritz Haber Institute, Max Planck Society;

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Citation

Ghan, S., Kunkel, C., Reuter, K., & Oberhofer, H. (2020). Improved Projection-Operator Diabatization Schemes for the Calculation of Electronic Coupling Values. Journal of Chemical Theory and Computation, 16(12), 7431-7443. doi:10.1021/acs.jctc.0c00887.


Cite as: http://hdl.handle.net/21.11116/0000-0007-6A91-E
Abstract
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.