학술논문
Monitoring the evolution of relative product populations at early times during a photochemical reaction
Document Type
Working Paper
Author
Nunes, Joao Pedro Figueira; 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, Nate; Hansen, Christopher S.; Hoffmann, Matthias; Holland, David M. P.; Ingle, Rebecca A.; Luo, Duan; Muvva, Sri Bhavya; Reid, Alex; 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.
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Subject
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Abstract
Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps towards understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species amongst the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations 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 3-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.