Time-Dependent Multiconfigurational Short-Range Density Functional Theory with Generalized Valence Bond Wave Functions

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, 174102], which employs direct Hessian techniques for both wave function optimization and linear response. We benchmark the performance of TD-GVB-srDFT for singlet and triplet excitation energies, as well as indirect spin-spin coupling constants (SSCCs). Compared to the underlying GVB-PP model, the method significantly improves excitation energies and achieves accuracy comparable to the complete active space variant, CAS-srDFT, with mean absolute deviations of 0.2 eV. The use of the generalized Tamm-Dancoff approximation (gTDA) is mandatory for reliable treatment of triplet excitations. For organic molecules, SSCCs computed with GVB-srDFT closely match those from CAS-srDFT and HF-srDFT results, whereas pure GVB-PP performs markedly worse than CASSCF for all coupling terms. Both GVB-srDFT and CAS-srDFT accurately reproduce fluorine-metal couplings in transition metal complexes, provided that gTDA is applied to singlet contributions.

Ce résumé expose les affirmations des auteurs. BNTIC ne l’interprète pas comme une validation indépendante des résultats.