Photoexcitation of 2-bromo-2-chloro-1,1,1-trifluoroethane (halothane) to repulsive surface nσ∗(C-Br) at 234 nm: Dynamics of C-Br and C-Cl bond rupture

► Photodissociation of halothane at 234 nm is reported. ► REMPI detection of Br(2P3/2,1/2) and Cl(2P3/2,1/2) fragments; the former channel is predominant. ► The bromine and chlorine fragments have one and two velocity components, respectively. ► Anisotropic distributions of bromine and chlorine fragments observed. ► A diabatic crossing from the nσ∗(C-Br) surface to nσ∗(C-Cl) diabatic surface is responsible for chlorine formation.