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Updated: May 12, 2026

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Photodeactivation paths in norbornadiene
1Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, P.O.B. 180, HR-10002, Zagreb, Croatia. iantol@emma.irb.hr
Quantum-chemical calculations reveal new photodeactivation pathways for norbornadiene. A doubly excited state facilitates ultrafast radiationless decay to the ground state, offering insights into molecular excited-state dynamics.
Area of Science:
- Computational Chemistry
- Photochemistry
- Quantum Mechanics
Background:
- Norbornadiene is a key molecule in photochemical studies.
- Understanding excited states is crucial for predicting molecular behavior.
Purpose of the Study:
- To perform high-level ab initio quantum-chemical calculations on norbornadiene's excited states.
- To elucidate potential energy surfaces (PESs) and deactivation pathways.
Main Methods:
- Utilized multireference configuration interaction with singles (MR-CIS) for optimization.
- Employed multiconfigurational second-order perturbation (CASPT2) for energy recalculations.
- Investigated stationary points, including minima and conical intersections.
Main Results:
- Identified crossing between valence V2 and Rydberg R1 states near the Franck-Condon (FC) point, enabling easy population switching.
- Proposed a novel photodeactivation pathway involving a doubly excited (DE) state.
- Found that R1/DE and DE/V1 conical intersections facilitate deactivation via the DE state.
- Characterized an Olivucci-Robb-type conical intersection for V1 to ground state deactivation.
Conclusions:
- The proposed deactivation pathways, with negligible barriers, allow for ultrafast radiationless decay.
- These findings provide a deeper understanding of norbornadiene's excited-state dynamics and photochemistry.
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