Multistate Density Functional Theory for Local and Charge-Transfer Tripdoublet States from Triplet-Free Radical Interactions

Chenyu Liu; Yang Xu; Peng Bao; Yangyi Lu; Jiali Gao

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arXiv · 2503.17559

Multistate Density Functional Theory for Local and Charge-Transfer Tripdoublet States from Triplet-Free Radical Interactions

Chenyu Liu·Yang Xu·Peng Bao·Yangyi Lu·Jiali Gao

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Abstract

The interaction between excited states of a closed-shell chromophore and a nearby free radical species gives rise to spin-coupled doublet states, namely singdoublet and tripdoublet, as well as a quartet state. This coupling facilitates transitions that are otherwise spin-forbidden, thereby enhancing intersystem crossing and influencing luminescence and non-radiative decay pathways. In this chapter, we explore these interactions using multistate density functional theory (MSDFT). By employing a minimal active space (MAS) comprising just ten determinant configurations, MSDFT effectively captures local and charge-transfer excitations with inclusion of correlation effects. MSDFT extends the Hohenberg-Kohn density functional theory from the ground state to encompass all electronic states, underscoring the potential for developing computationally efficient methods to study excited states. Numerical results demonstrate that MSDFT accurately reproduces both qualitative trends and quantitative excited-state energies, in accord with previous studies using extended multistate complete-active-space second-order perturbation theory (XMS-CASPT2). The work explores energy changes along a reaction path from the D_0/D_1 minimum energy crossing intersection to the D_2/D_3 crossing in the exciplex formed by 10-methylphenothiazine and a dicarboximide electron acceptor linked to the stable free radical 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO).

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Chenyu Liu, Yang Xu, Peng Bao, Yangyi Lu, Jiali Gao. 2025-03-21. Multistate Density Functional Theory for Local and Charge-Transfer Tripdoublet States from Triplet-Free Radical Interactions. https://arxiv.org/abs/2503.17559

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