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How Symmetry Governs the Dihedral Angle Dependence of Intermolecular Spin-Orbit Coupling

Chemical Physics 2026-04-08 v2

Abstract

Spin-orbit, charge-transfer intersystem crossing (SOCT-ISC) allows for the efficient production of triplet excited states in donor-acceptor (DA) dyads without the involvement of heavy atoms, for use in a myriad of technologies. This process is commonly believed to proceed optimally when the dihedral angle between donor and acceptor moieties is orthogonal. Here, we challenge this idea through a theoretical study unveiling a scenario where spin-orbit couplings (SOCs) are minimized under orthogonal conditions. This scenario is rationalized based on an analysis of the structure-imposed symmetry properties of the involved singlet and triplet states. Notably, in this scenario, finite SOCs demand oblique orientation angles, which in turn requires molecular chirality, suggesting chirality to be a prerequisite for activating the involved SOC pathways.

Keywords

Cite

@article{arxiv.2603.28961,
  title  = {How Symmetry Governs the Dihedral Angle Dependence of Intermolecular Spin-Orbit Coupling},
  author = {Antonio J. Garzon-Ramirez and Connor K. Terry Weatherly and Kyle T. Kairys and Michael R. Wasielewski and Roel Tempelaar},
  journal= {arXiv preprint arXiv:2603.28961},
  year   = {2026}
}

Comments

8 pages, 4 figures