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

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Muvva, Sri Bhavya, Liu, Yusong, Chakraborty, Pratip, Nunes, Joao Pedro Figueira, Attar, Andrew R., Bhattacharyya, Surjendu, Borne, Kurtis, Champenois, Elio G., Goff, Nathan, Hegazy, Kareem, Hoffmann, Matthias C., Ji, Fuhao, Lin, Ming-Fu, Luo, Duan, Ma, Lingyu, Odate, Asami, Pathak, Shashank, Rolles, Daniel, Rudenko, Artem, Saha, Sajib Kumar, Shen, Xiaozhe, Wang, Xijie, Ware, Matthew R., Weathersby, Stephen, Weber, Peter M., Wilkin, Kyle J., Wolf, Thomas J. A., Xiong, Yanwei, Xu, Xuan, Yang, Jie, Matsika, Spiridoula, Weinacht, Thomas and Centurion, Martin (2024) Ultrafast structural dynamics of UV photoexcited cis,cis-1,3-cyclooctadiene observed with time-resolved electron diffraction. Physical Chemistry Chemical Physics, 27 (1). pp. 471-480. ISSN 1463-9076

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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 cis,cis-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.

Item Type:	Article
Additional Information:	Data availability statement: The data supporting this article is available at Zenodo at the following link: https://doi.org/10.5281/zenodo.12720149. Funding information: The SLAC MeV UED facility is supported in part by the US Department of Energy, Office of Basic Energy Sciences, SUF Division Accelerator & Detector R&D program, the Linac Coherent Light Source Facility, and SLAC under contract no. DE-AC02-05-CH11231 and DE-AC02-76SF00515. SBM, JPFN, SB, SKS, KJW, YX, AR, DR, and MC were funded through the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy under DOE-EPSCoR grant no. DE-SC0020276. SP and KB were funded by the US Department of Energy under grant no. DE-FG02-86ER1349. NG, AO, and PMW were funded by the US Department of Energy under grant no. DE-SC0017995. SM and PC acknowledge support from DOE, Award no. DE-FG02-08ER15983. TW and YL acknowledge support from DOE, Award No. DE-FG02-08ER15984. The computational work was performed using the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant no. ACI-1548562.
Faculty \ School:	Faculty of Science > School of Chemistry, Pharmacy and Pharmacology
Related URLs:	http://www.scopus.com/inward/record.url?... https://xlink.rsc.org/?DOI=D4CP02785J
Depositing User:	LivePure Connector
Date Deposited:	14 Dec 2024 01:39
Last Modified:	28 Jan 2025 23:44
URI:	https://ueaeprints.uea.ac.uk/id/eprint/97991
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