Measurement of time dependent product branching ratios indicates two-state reactivity in metal mediated chemical reactions

Abstract

For several decades, the influence of Two State Reactivity (TSR) has been implicated in a host of reactions, but has lacked a stand-alone, definitive experimental kinetic signature identifying its occurrence. Here, we demonstrate that the measurement of a temporally dependent product branching ratio is indicative of spin inversion and is a kinetic signature of TSR. This is caused by products exiting different hypersurfaces with different rates and relative exothermicities. The composite measurement of product intensities with the same mass but with different multiplicities yield biexponential temporal dependences with the sampled product ratio changing in time. These measurements are made using the single photon initiated dissociative rearrangement reaction (SPIDRR) technique which identifies TSR but further determines the kinetic parameters for reaction along the original ground electronic surface in competition with spin inversion and its consequent TSR.