Ultrafast structural dynamics of UV photoexcited <i>cis</i>,<i>cis</i>-1,3-cyclooctadiene observed with time-resolved electron diffraction

Conjugated diene molecules are highly reactive upon photoexcitation and can relax through multiple reaction channels that depend on the position of the double bonds and the degree of molecular rigidity. Understanding the photoinduced dynamics of these molecules is crucial for establishing general rules governing the relaxation and product formation. Here, we investigate the femtosecond time-resolved photoinduced excited-state structural dynamics of <i>cis</i>,<i>cis</i>-1,3-cyclooctadiene, a large-flexible cyclic conjugated diene molecule, upon excitation with 200 nm using mega-electron-volt ultrafast electron diffraction and trajectory surface hopping dynamics simulations. We tracked the photoinduced structural changes from the Franck-Condon region through the conical intersection seam to the ground state. Our findings revealed a novel primary reaction coordinate involving ring distortion, where the ring stretches along one axis and compresses along the perpendicular axis. The nuclear wavepacket remains compact along this reaction coordinate until it reaches the conical intersection seam, and it rapidly spreads as it approaches the ground state, where multiple products are formed.

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Publication Details

Journal
Physical Chemistry Chemical Physics
Published
2024-12-03
DOI
https://doi.org/10.1039/d4cp02785j
Citations
9
Primary Topic
Photochemistry and Electron Transfer Studies
Type
article
Field-Weighted Citation Impact
4.00

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article

Ultrafast structural dynamics of UV photoexcited cis,cis-1,3-cyclooctadiene observed with time-resolved electron diffraction

Elio G. Champenois, Daniel Rolles, Stephen Weathersby, Asami Odate et al.
9 citations
Physical Chemistry Chemical Physics
Photochemistry and Electron Transfer Studies
4.00
article

Ultrafast structural dynamics of UV photoexcited cis,cis-1,3-cyclooctadiene observed with time-resolved electron diffraction

Elio G. Champenois, Daniel Rolles, Stephen Weathersby, Asami Odate, Matthias C. Hoffmann, Surjendu Bhattacharyya, Fuhao Ji, Xiaozhe Shen, Martin Centurion, Sri Bhavya Muvva, Pratip Chakraborty, Ming‐Fu Lin, Sajib Kumar Saha, Thomas Weinacht, Xuan Xu, Duan Luo, Artem Rudenko, Spiridoula Matsika, Kareem Hegazy, Peter Weber, Andrew Attar, Shashank Pathak, Yanwei Xiong, Thomas Wolf, Xijie Wang, Kyle Wilkin, Nathan Goff, Kurtis Borne, Jie Yang, Yusong Liu, J. Pedro F. Nunes, Lingyu Ma, Matthew R. Ware
article en
9 citations

Abstract

Conjugated diene molecules are highly reactive upon photoexcitation and can relax through multiple reaction channels that depend on the position of the double bonds and the degree of molecular rigidity. Understanding the photoinduced dynamics of these molecules is crucial for establishing general rules governing the relaxation and product formation. Here, we investigate the femtosecond time-resolved photoinduced excited-state structural dynamics of <i>cis</i>,<i>cis</i>-1,3-cyclooctadiene, a large-flexible cyclic conjugated diene molecule, upon excitation with 200 nm using mega-electron-volt ultrafast electron diffraction and trajectory surface hopping dynamics simulations. We tracked the photoinduced structural changes from the Franck-Condon region through the conical intersection seam to the ground state. Our findings revealed a novel primary reaction coordinate involving ring distortion, where the ring stretches along one axis and compresses along the perpendicular axis. The nuclear wavepacket remains compact along this reaction coordinate until it reaches the conical intersection seam, and it rapidly spreads as it approaches the ground state, where multiple products are formed.

Physical Chemistry Chemical PhysicsVol. 27(1)
University of East Anglia (GB), University of Nebraska–Lincoln (US), Kansas State University (US), Brown University (US), SLAC National Accelerator Laboratory (US), Stony Brook University (US), Temple University (US), Stanford University (US)
National Science Foundation, U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Office of Experimental Program to Stimulate Competitive Research, SLAC National Accelerator Laboratory
Openalex Percentile: Top 5%
Photochemistry and Electron Transfer Studies
4.00
DOIOpen Access PDFOpenAlex
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