Abstract
One of the grand challenges in chemistry has been to directly observe atomic motions during chemical processes. The depiction of the nuclear configurations in space-time to understand barrier crossing events has served as a unifying intellectual theme connecting the different disciplines of chemistry. This challenge has been cast as an imaging problem in which the technical issues reduce to achieving not only sufficient simultaneous space-time resolution but also brightness for sufficient image contrast to capture the atomic motions. This objective has been met with electrons as the imaging source. The review chronicles the first use of electron structural probes to study reactive intermediates, to the development of high bunch charge electron pulses with sufficient combined spatial-temporal resolution and intensity to literally light up atomic motions, as well as the means to characterize the electron pulses in terms of temporal brightness and image reconstruction. The use of femtosecond Rydberg spectroscopy as a novel means to use internal electron scattering within the molecular reference frame to obtain similar information on reaction dynamics is also discussed. The focus is on atomically resolved chemical reaction dynamics with pertinent references to work in other areas and forms of spectroscopy that provide additional information. Effectively, we can now directly observe the far-from-equilibrium atomic motions involved in barrier crossing and categorize chemistry in terms of a power spectrum of a few dominant reaction modes. It is this reduction in dimensionality that makes chemical reaction mechanisms transferrable to seemingly arbitrarily complex (large N) systems, up to molecules as large as biological macromolecules (N > 1000 atoms). We now have a new way to reformulate reaction mechanisms using an experimentally determined dynamic mode basis that in combination with recent theoretical advances has the potential to lead to a new conceptual basis for chemistry that forms a natural link between structure and dynamics.
Highlights
Time-Dependent Diffraction from Single Crystals3. Path to Atomically Resolved Reaction Dynamics 3.1
Chemists’ Gedanken Experiment: Challenge and Intellectual ObjectivesOne of the dream experiments in chemistry is to directly observe atomic motions in real time during chemical reactions.[1,2] Chemistry after all involves structural dynamics by definition, and to observe the interconversion of molecules from one structure to another would capture the very essence of chemistry
The review chronicles the first use of electron structural probes to study reactive intermediates, to the development of high bunch charge electron pulses with sufficient combined spatial-temporal resolution and intensity to literally light up atomic motions, as well as the means to characterize the electron pulses in terms of temporal brightness and image reconstruction
Summary
3. Path to Atomically Resolved Reaction Dynamics 3.1. Molecular Alignment: Prospect for Improved Structural Determination for Gas Phase Systems 3.3. Scaling to Larger Systems: Electrocyclic Ring-Opening Reaction of 1,3-Cyclohexadiene. 4. Breaking the Picosecond Barrier to Atomically Resolved Dynamics 4.1. Development of Ultrabright Femtosecond Electron Sources High Brightness, Nonrelativistic Electrons Relativistic Electrons 4.2. Realization of Atomically Resolved Reaction Dynamics: Imaging Chemistry in Action 4.3. Alternative Electron Imaging of Reaction Dynamics: Rydberg Spectroscopy: Looking from the Inside Out
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