Spin-Flip TDDFT with Noncollinear Kernels and Its Application on Low-Lying Excited States

Abstract: Spin-flip time-dependent density functional theory (TDDFT) employing a noncollinear kernel constitutes a promising methodology for the characterization of electronic states within complex molecular systems. In the present study, we examine three challenging practical scenarios: (1) States that are mainly dominated by a double excitation configuration, where spin-conserving TDDFT can't reach double excitation configurations due to its single excitation nature; (2) Singlet ground states that are contributed by multi-configurations in singlet diradicals and diradicaloids, where DFT meets difficulties due to its single determinant nature; (3) Inverted energy gap between the first singlet excited state and the lowest triplet state when Hund's rule is violated, which is experimentally found in thermally activated delayed fluorescence (TADF) molecules. Spin-conserving TDDFT has been shown to fail in such a situation. Notably, we can predict the inverted energy gap in TADF molecules with GGA, mGGA and hybrid functionals. We demonstrate the accuracy and robustness of spin-flip TDDFT when applied to these demanding contexts. Furthermore, we elucidate the nature of the electronic configurations underpinning these phenomena, which can facilitate further advancements in the development of these functional molecules.