Probing Conical Intersection in the Multipathway Isomerization of CH₃Cl Using Coulomb Explosion

Ubiquitous ultrafast isomerization is paramount in photoexcited molecules, in which non-adiabatic coupling among multiple electronic states can occur. We use the pump–probe Coulomb explosion imaging method to study the isomerization of CH₃Cl molecules. We find that the isomerization under our strong field pump–probe scheme proceeds along multiple pathways, which are encoded in several distinct branches of the time-resolved kinetic energy release spectra for the CH₂⁺+HCl⁺ Coulomb explosion channel. Apart from the isomerized dissociative pathway in neutral and cationic excited states, the pump laser can also induce coherent vibrational dynamics in two coupled intermediate states and set up the initial conditions for the two concurrently proceeding isomerization pathways. The isomerization of CH₃Cl provides an intriguing example of a chemical reaction consisting of multiple pathways and non-adiabatic dynamics.