Ultrafast dynamics and excited-state trapping in [3.3]paracyclophane
Abstract
, where it becomes kinetically trapped. Analysis of the fragment-based transition density matrix reveals a concurrent transformation of the electronic structure-from an excitonic-resonance state with minor charge-transfer (CT) character (≈0.2) to a mixed excitonic/charge-resonance regime with CT ≈ 0.5. This evolution is accompanied by a structural contraction of the π-stack, as the two benzene rings approach each other, activating an inter-ring breathing motion that governs the subsequent dynamics. Because [3.3]PCP combines rapid nonadiabatic relaxation with long-lived excited-state trapping, it serves as a particularly demanding benchmark for trajectory-based dynamics methods, offering both a mechanistic picture of excimer formation and a stringent test of their current capabilities.
Fields of Study & Subjects
Synthesis and Properties of Aromatic Compounds
Supramolecular Chemistry and Complexes
Magnetism in coordination complexes
Publication details
- Journal / source
- Physical Chemistry Chemical Physics
- Publisher
- Royal Society of Chemistry (RSC)
- Volume
- 28
- Issue
- 6
- Pages
- 4177–4187
- Publication date
- 1 January 2026
- Language
- EN