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arXiv · 2310.05100

Role of Centrosymmetry in the Photophysics of Molecular Aggregates

Qingyun Wan·Chi-Ming Che
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Abstract

To understand the photophysics of molecular aggregates, exciton model of J- and H-aggregate has been extensively utilized. However, it lacks consideration of crystal symmetry. Although discrete molecules may lack symmetry, their aggregates can exhibit a high degree of symmetry. Herein, we utilized group theory to study the optical properties of centrosymmetric molecular aggregates, showing that their optical selection rules (transition dipole moment and spin-orbit coupling) are determined by the symmetry of singlet and triplet excited states and the intermolecular orbital overlap. Symmetry-forbidden electronic transitions are closely related to ultralong organic phosphorescence. Our model's scope is broad, as over 50% of organic crystals belong to centrosymmetric space groups according to Cambridge Structural Database.

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Qingyun Wan, Chi-Ming Che. 2023-10-08. Role of Centrosymmetry in the Photophysics of Molecular Aggregates. https://arxiv.org/abs/2310.05100

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