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Related Experiment Video

Updated: Jun 5, 2025

Experimental Investigation of Secondary Flow Structures Downstream of a Model Type IV Stent Failure in a 180° Curved Artery Test Section

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Vibronic Conical Intersection Trajectory Signatures in Wave Packet Coherences.

Indranil Ghosh^1,2,3,4, Qijie Shen^1,2,3,4, Ping-Jui Eric Wu^1,2,3,4

¹Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.

The Journal of Physical Chemistry Letters

|December 13, 2024

Summary

Researchers observed nonadiabatic dynamics in Wurster's Blue using 2D electronic spectroscopy. They revealed distinct relaxation pathways through conical intersections, crucial for understanding photochemical reactions.

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Last Updated: Jun 5, 2025

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Published on: July 19, 2016

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Area of Science:

Chemical Physics
Spectroscopy
Photochemistry

Background:

Conical intersections are fundamental to chemical system energy landscapes and photochemical reactivity.
Observing these conical intersections spectroscopically presents significant challenges.

Purpose of the Study:

To investigate the nonadiabatic dynamics of Wurster's Blue following excitation to its lowest two vibronic excited states.
To elucidate the role of conical intersections in molecular relaxation and intramolecular electron transfer.

Main Methods:

Utilized two-dimensional electronic spectroscopy (2DES) to probe ultrafast dynamics.
Analyzed coherent oscillations and relaxation pathways after excitation.

Main Results:

Observed ballistic relaxation through a conical intersection in 55 fs to the ground electronic state.
Identified identical kinetics but distinct coherent oscillation patterns post-conical intersection traversal.
Demonstrated that coherences arise from dynamical trajectories projecting onto the conical intersection's vibrational space, not direct pulse excitation.

Conclusions:

Spectroscopic data provides new insights into conical intersection topology and dynamics.
The intersection space critically influences the dictation of molecular dynamics.
Distinct relaxation pathways are governed by how trajectories interact with the conical intersection's vibrational modes.