학술논문
Monitoring the Evolution of Relative Product Populations at Early Times during a Photochemical Reaction
Document Type
Article
Author
Figueira Nunes, Joao Pedro; Ibele, Lea Maria; Pathak, Shashank; Attar, Andrew R.; Bhattacharyya, Surjendu; Boll, Rebecca; Borne, Kurtis; Centurion, Martin; Erk, Benjamin; Lin, Ming-Fu; Forbes, Ruaridh J. G.; Goff, Nathan; Hansen, Christopher S.; Hoffmann, Matthias; Holland, David M. P.; Ingle, Rebecca A.; Luo, Duan; Muvva, Sri Bhavya; Reid, Alexander H.; Rouzée, Arnaud; Rudenko, Artem; Saha, Sajib Kumar; Shen, Xiaozhe; Venkatachalam, Anbu Selvam; Wang, Xijie; Ware, Matt R.; Weathersby, Stephen P.; Wilkin, Kyle; Wolf, Thomas J. A.; Xiong, Yanwei; Yang, Jie; Ashfold, Michael N. R.; Rolles, Daniel; Curchod, Basile F. E.
Source
Journal of the American Chemical Society; February 2024, Vol. 146 Issue: 6 p4134-4143, 10p
Subject
Language
ISSN
00027863; 15205126
Abstract
Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps toward understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species among the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initiomolecular dynamics calculations offer a powerful route to determining time-resolvedpopulations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (∼50%) yield of an episulfide isomer containing a strained three-membered ring within ∼1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.