2018 Volume 94 Issue 10 Pages 428-440
Single-molecule atomic-resolution real-time electron microscopic movie imaging is an emerging new tool for obtaining dynamic structural information on molecules and molecular assemblies. This method provides a hitherto inaccessible possibility to in situ observe the time evolution of chemical events at various temperatures from the beginning till the end, as demonstrated for the kinetics study of [2 + 2] cycloaddition of [60]fullerene molecules, which was found to occur via an excited state or via radical cation depending on the temperature. One unique feature of this methodology is that, by observing directly the reaction events, one can obtain information on the frequency of events unperturbed by molecular diffusion. With the obtained experimental data set, we provided the first experimental proof of what the quantum mechanical transition state theory predicted, in that isolated molecules behave as if all their accessible states were occupied in a random order. We also found that, under the 1-D reaction conditions, molecular-level information on a few hundred molecules suffices to deduce statistically meaningful kinetics data that match with those obtained by bulk experiments.
