Understanding Electron Beam-Induced Chemical Polymerization Processes of Small Organic Molecules Using Operando Liquid-Phase Transmission Electron Microscopy

Electron beams evolved as important tools for modern technologies that construct and analyze nanoscale architectures. While electron-matter interactions at atomic and macro scales are well-studied, a knowledge gap persists at the molecular to nano level─the scale most relevant to the latest technologies. Here, we employ <i>operando</i> liquid-phase transmission electron microscopy supported by density functional theory calculations and a mathematical random search algorithm to rationalize and quantify electron beam-induced processes at the molecular level. By examining a series of small organic molecules, we identify critical physical and chemical parameters that dictate polymerization rates under continuous electron beam irradiation. Our findings offer a deeper understanding of electron beam-induced reactions, enabling the prediction of molecular reactivities from a classical chemistry perspective. These insights apply equally to other soft matter systems and, thus, are of fundamental interest to scientists and engineers who use electron beams to analyze or to manipulate nanoscale matter.