arXiv subjects

Connor K. Terry Weatherly

Publications and source records attributed to Connor K. Terry Weatherly.

3 recordsLinked to original sources

arXiv2026

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

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.

physics.chem-ph↗

arXiv2025

Optically Addressing Circularly-Polarized Vibrations in Molecules

Circularly-polarized (CP) vibrations are the nuclear-motion analog of CP light, emerging in molecules with non-Abelian point-group symmetry that support orthogonal and degenerate vibrational normal modes. Here, we explore the optical addressability of CP vibrations, motivated by their potential as nanoscale angular momentum states suitable for information storage and manipulation. We investigate how symmetry-breaking chemical modifications affect a molecule's capacity to support CP vibrations. Notably, we find cases where modes retain their orthogonality and degeneracy in spite of such modifications, broadening the opportunities afforded by CP vibrations beyond non-Abelian point-group molecules. Prospects for experimental implementations using CP pump-probe techniques are briefly discussed.

physics.chem-ph↗

arXiv2022

UV/vis-to-IR Photonic Down Conversion Mediated by Excited State Vibrational Polaritons

This work proposes a new photophysical phenomenon whereby UV/vis excitation of a molecule involving a Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated by vibrational polaritons in the electronic excited state potential. It is shown that the formation of such excited state vibrational polaritons (ESVP) via UV/vis excitation only occurs with molecules having vibrational modes with both a non-zero FC activity and IR activity in the excited state. Density functional theory calculations are shown to effectively identify a candidate molecule, 1-Pyreneacetic acid (PAA), with this property and the dynamics of ESVP are modeled using the truncated Wigner approximation. Overall, this work presents a new avenue of polariton chemistry where excited state dynamics, driven by photoexcitation, are influenced by the formation of vibrational polaritons. Along with this, the photonic down conversion is potentially useful in both the sensing of excited state vibrations and in quantum transduction schemes.

physics.chem-ph↗