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oai:figshare.com:article/33945344 2026-09-20T14:06:18Z category_1 category_4 category_13 category_14 category_15 category_873 portal_63 item_type_3 month_year_09_2026

The Role of Charge Transfer and Parity Symmetry of the Wave Function in N,N′‑Bis(2-phenylethyl)-3,4,9,10-perylenedicarboximide Crystals: A Frenkel-Holstein Approach Xin Chang (741323) Wennie Wang (8610264) Biophysics Biochemistry Genetics Molecular Biology Neuroscience Chemical Sciences not elsewhere classified phenylethyl )- 3 model reproduces polymorph matched chain |< level design rules even (+) sector ep – pdi dependent vibronic ratios ></ sub >. >< sub >< triplet yield via holstein approach charge tuning tt visibility explicitly includes ct active ct state mediated tt participation hole transfer coupling triplet pair mediated superexchange hole transfer charge transfer tt signatures suppressing ct ct features tt </ ct </ wave function singlet fission relative phases provides packing often weak efficient pathway condon limit >′- bis Charge-transfer (CT) configurations can provide an efficient pathway to the triplet pair (TT) manifold in singlet fission (SF), yet diagnosing CT-mediated TT participation from optical spectra remains challenging because TT signatures are often weak, obscured, or missing. Here, we develop an extended Frenkel–Holstein Hamiltonian that explicitly includes CT and intermolecular TT diabatic states. We show that site-exchange parity controls optical activity. In the Condon limit, only the even (+) sector is bright, and TT borrows oscillator strength only through the parity-matched chain |<i>FE</i>₊⟩ →|<i>CT</i>₊⟩ → |<i>TT</i>₊⟩ off the Frenkel exciton (FE) as determined by the relative phase of the electron/hole transfer coupling <i>t</i>₊ and relative phase of the CT–TT coupling <i>g</i>_<i>+</i>. CT–TT mixing also raises the energy of the active CT state, increasing the effective FE–CT detuning and suppressing CT-mediated superexchange. When applied to the α- and β-phase <i>N</i>,<i>N</i>′-bis(2-phenylethyl)-3,4,9,10-perylenedicarboximide (EP–PDI) crystals, the model reproduces polymorph-dependent vibronic ratios and CT features and provides packing-level design rules for tuning TT visibility and triplet yield via the relative phases of electron/hole transfer and CT–TT exchange couplings. 2026-09-20T00:00:00Z Dataset Dataset 10.1021/acs.jpclett.6c01908.s002 https://figshare.com/articles/dataset/The_Role_of_Charge_Transfer_and_Parity_Symmetry_of_the_Wave_Function_in_N_N_Bis_2-phenylethyl_-3_4_9_10-perylenedicarboximide_Crystals_A_Frenkel-Holstein_Approach/33945344 CC BY-NC 4.0