Monitoring the Evolution of Relative Product Populations at Early Times during a Photochemical Reaction

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 <i>ab initio</i> molecular dynamics calculations offer a powerful route to determining <i>time-resolved</i> populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5<i>H</i>)-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.