Monitoring the evolution of relative product populations at early times during a photochemical reaction
Creators
- Figueira Nunes, Joao Pedro1
- Hoffmann, Matthias2
- Attar, Andrew2
- Shen, Xiaozhe2
- Luo, Duan2
- Muvva, Sri Bhavya1
- Rudenko, Artem3
- Venkatachalam, Anbu3
- Boll, Rebecca4
- Wang, Xijie2
- Xiong, Yanwei1
- Saha, Sajib Kumar1
- Borne, Kurtis3
- Bhattacharyya, Surjendu3
- Wilkin, Kyle1
- Hansen, Christopher5
- Yang, Jie2
- Forbes, Ruaridh2
- Ibele, Lea M.6
- Rouzee, Arnaud7
- Centurion, Martin1
- Lin, Ming-Fu2
- Goff, Nathan8
- Weathersby, Stephen2
- Erk, Benjamin9
- Wolf, Thomas2
- Pathak, Shashank3
- Ware, Matthew2
- Reid, Alex2
- Ingle, Rebecca10
- Ashfold, Michael11
- Holland, David12
- Rolles, Daniel3
- Curchod, Basile11
- 1. University of Nebraska–Lincoln
- 2. SLAC National Accelerator Laboratory
- 3. Kansas State University
- 4. European X-Ray Free-Electron Laser
- 5. University of New South Wales
- 6. University of Paris-Saclay
- 7. Max-Born-Institute for Nonlinear Optics and Short Pulse Spectroscopy
- 8. Brown University
- 9. Deutsches Elektronen-Synchrotron DESY
- 10. University College London
- 11. University of Bristol
- 12. Daresbury Laboratory
Description
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 offers a unique route to determine time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule thiophenone. This strategy reveals an unexpectedly high (~50%) yield of an episulfide isomer containing a strained 3-membered ring within ~1 ps at early times and rapid interconversions between the rival photoproducts.