Since the discovery of electron-wave duality, electron scattering instrumentation has developed into a powerful array of techniques for revealing the atomic structure of matter. Beyond detecting local lattice variations in equilibrium structures with the highest possible spatial resolution, recent research e↵orts have been directed towards the long sought-after dream of visualizing the dynamic evolution of matter in real-time. The atomic behavior at ultrafast timescales carries critical information on phase transition and chemical reaction dynamics, the coupling of electronic and nuclear degrees of freedom in materials and molecules, the correlation between structure, function and previously hidden metastable or nonequilibrium states of matter. Ultrafast electron pulses play an essential role in this scientific endeavor, and their generation has been facilitated by rapid technical advances in both ultrafast laser and particle accelerator technologies. This review presents a summary of the remarkable developments in this field over the last few decades. The physics and technology of ultrafast electron beams is presented with an emphasis on the figures of merit most relevant for ultrafast electron di↵raction (UED) experiments. We discuss recent developments in the generation, manipulation and characterization of ultrashort electron beams aimed at improving the combined spatio-temporal resolution of these measurements. The fundamentals of electron scattering from atomic matter and the theoretical frameworks for retrieving dynamic structural information from solid-state and gas-phase samples is described. Essential experimental techniques and several landmark works that have applied these approaches are also highlighted to demonstrate the widening applicability of these methods. Ultrafast electron probes with ever improving capabilities, combined with other complementary photonbased or spectroscopic approaches, hold tremendous potential for revolutionizing our ability to observe and understand energy and matter at atomic scales.

Conformer-specific dynamics Conformation-dependent dynamics play an important role in organic chemistry syntheses such as electrocyclic reactions, as well as in biological processes such as protein folding. However, current time-resolved experimental methods struggle to distinguish conformers from each other, and conformational isomerism is usually analyzed through reactant and product distributions. Using a combination of mega–electron volt ultrafast electron diffraction and quantum wave packet simulations, Champenois et al . directly followed the photochemical electrocyclic ring opening of the molecule α-phellandrene with femtosecond time resolution and confirmed that the transformation of a specific molecular conformer follows the famous Woodward-Hoffmann rules. The proposed method is potentially a powerful tool to follow conformer specificity in various organic and biological systems in real time. —YS

The roughness is a common property of all growing surfaces – however, the way the roughness of a growing surface changes with time and space is uniquely related to the underlying growth process, i.e. to how the atoms stick to the surface during the first stage of nucleation. This concept allows getting insights on the nucleation process of a growing surface by measuring two scaling exponents, α and β, known as roughness and growth exponents, respectively. In this work, we studied hydrogenation of graphene using the roughening kinetics. The coverage of graphene will depend on how the H ions stick on the surface, giving rise to a unique roughness evolution in time and space. We measured a roughness exponent of ~0.5 (derived from a Fourier index of ~3), and a growth exponent of ~0.3. The values of the growth and roughness exponents are close to those reported for clustered carbon, suggesting a roughening mechanism by clustering, in good agreement with the theory. We also compared our coverage data with a different model, used to describe the dynamics of graphene coverage, during chemical vapour deposition. Our data are in agreement with a nucleation-dominated growth, further confirming that hydrogenation is happening by clustering.

Many important biological and chemical processes are initiated by the transfer of a proton from a donor to an acceptor group within a molecule and are regulated by the interplay of nuclear and electronic dynamics. The electronic dynamics of proton transfer are well-studied, yet the nuclear dynamics have never been spatiotemporally resolved. Herein, we present a direct observation of the nuclear motions leading to and ensuing from photochemical proton transfer in o-nitrophenol using ultrafast electron diffraction. The proton transfer step is identified by the transient compression of the donor-acceptor distance and captured on the femtosecond timescale with sub-Angstrom resolution. Supported by ab initio multiple spawning simulations, our observations uncover the structural changes mediating excited-state relaxation. Our work provides an unprecedented mechanistic insight into the photochemical proton transfer mechanism and photo-relaxation dynamics of o-nitrophenol, unambiguously connecting an experimental observable to a process previously confined to theoretical models.

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