Summary form only given. Fundamental processes in atoms, molecules, as well as condensed matter are triggered or mediated by the motion of electrons inside or between atoms. Electronic dynamics on atomic length scales tends to unfold within tens to thousands of attoseconds (1 attosecond [as] = 10-18 s). Recent breakthroughs in laser science are now opening the door to watching and controlling these hitherto inaccessible microscopic dynamics. The key to accessing the attosecond time domain is the control of the electric field of (visible) light, which varies its strength and direction within less than a femtosecond (1 femtosecond = 1000 attoseconds). Atoms exposed to a few oscillations cycles of intense laser light are able to emit a single extreme ultraviolet (XUV) burst lasting less than one femtosecond. Full control of the evolution of the electromagnetic field in laser pulses comprising a few wave cycles have recently allowed the reproducible generation and measurement of isolated sub-femtosecond XUV pulses, demonstrating the control of microscopic processes (electron motion and photon emission) on an attosecond time scale. These tools have enabled us to visualize the oscillating electric field of visible light with an attosecond "oscilloscope", to control single-electron and probe multi-electron dynamics in atoms, molecules and solids. Recent experiments hold promise for the development of an attosecond X-ray source, which may pave the way towards 4D electron imaging with sub-atomic resolution in space and time.

Attosecond Physics

We used 600-femtosecond electron pulses to study the structural evolution of aluminum as it underwent an ultrafast laser–induced solid-liquid phase transition. Real-time observations showed the loss of long-range order that was present in the crystalline phase and the emergence of the liquid structure where only short-range atomic correlations were present; this transition occurred in 3.5picoseconds for thin-film aluminum with an excitation fluence of 70 millijoules per square centimeter. The sensitivity and time resolution were sufficient to capture the time-dependent pair correlation function as the system evolved from the solid to the liquid state. These observations provide an atomic-level description of the melting process, in which the dynamics are best understood as a thermal phase transition under strongly driven conditions.

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An Atomic-Level View of Melting Using Femtosecond Electron Diffraction

Ultrafast electron diffraction (UED) has been developed to study transient structures in complex chemical reactions initiated with femtosecond laser pulses. This direct imaging of reactions was achieved using our third-generation apparatus equipped with an electron pulse (1.07 ± 0.27 picoseconds) source, a charge-coupled device camera, and a mass spectrometer. Two prototypical gas-phase reactions were studied: the nonconcerted elimination reaction of a haloethane, wherein the structure of the intermediate was determined, and the ring opening of a cyclic hydrocarbon containing no heavy atoms. These results demonstrate the vastly improved sensitivity, resolution, and versatility of UED for studying ultrafast structural dynamics in complex molecular systems.

https://science.sciencemag.org/content/sci/291/5503/458.full.pdf

Direct imaging of transient molecular structures with ultrafast diffraction.

In this review, we highlight the progress made in the development of 4D ultrafast electron diffraction (UED), crystallography (UEC), and microscopy (UEM) with a focus on concepts, methodologies, and prototypical applications. The joint atomic-scale resolutions in space and time, and sensitivity reached, make it possible to determine complex transient structures and assemblies in different phases. These applications include studies of isolated chemical reactions (molecular beams), interfaces, surfaces and nanocrystals, self-assembly, and 2D crystalline fatty-acid bilayers. In 4D UEM, we are now able, using timed, single-electron packets, to image nano-to-micro scale structures of materials and biological cells. Future applications of these methods are foreseen across areas of physics, chemistry, and biology.

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4D ultrafast electron diffraction, crystallography, and microscopy.

One of the great dream experiments in Science is to directly observe atomic motions as they occur. Femtosecond electron diffraction provided the first 'light' of sufficient intensity to achieve this goal by attaining atomic resolution to structural changes on the relevant timescales. This review covers the technical progress that made this new level of acuity possible and gives a survey of the new insights gained from an atomic level perspective of structural dynamics. Atomic level views of the simplest possible structural transition, melting, are discussed for a number of systems in which both thermal and purely electronically driven atomic displacements can be correlated with the degree of directional bonding. Optical manipulation of charge distributions and effects on interatomic forces/bonding can be directly observed through the ensuing atomic motions. New phenomena involving strongly correlated electron?lattice systems are also discussed in which optically induced changes in the potential energy landscape lead to ballistic structural changes. Concepts such as the structural order parameters are now directly observable at the atomic level of inspection to give a remarkable view of the extraordinary degree of cooperativity involved in strongly correlated electron?lattice systems. These recent examples, in combination with time-resolved real space imaging now possible with electron probes, are truly defining an emerging field that holds great promise to make a significant impact in how we understand structural dynamics.This article is dedicated to the memory of Professor David John Hugh Cockayne, a world leader in electron microscopy, who sadly passed away in December.

https://iopscience.iop.org/article/10.1088/0034-4885/74/9/096101/pdf

Femtosecond electron diffraction: heralding the era of atomically resolved dynamics

With the advent of femtosecond (fs) time resolution in spectroscopic experiments, it is now possible to study the evolution of nuclear motions in chemical and photobiochemical reactions. In general, the reaction is clocked by an initial fs laser pulse (which establishes a zero of time) and the dynamics are probed by a second fs pulse; the detection methods include conventional and photoelectron spectroscopy and mass spectrometry. Replacing the probe laser with electron pulses offers a means for imaging ultrafast structural changes with diffraction techniques, which should permit the study of molecular systems of greater complexity (such as biomolecules). On such timescales, observation of chemical changes using electron scattering is non-trivial, because space-charge effects broaden the electron pulse width and because temporal overlap of the (clocking) photon pulse and the (probe) electron pulse must be established. Here we report the detection of transient chemical change during molecular dissociation using ultrafast electron diffraction. We are able to detect a change in the scattered electron beam with the zero of time established unambiguously and the timing of the changes clocked in situ. This ability to clock changes in scattering is essential to studies of the dynamics of molecular structures.

/pdf/clocking-transient-chemical-changes-by-ultrafast-electron-11o5tqy6zb.pdf

Hans Frey

Papers

Clocking transient chemical changes by ultrafast electron diffraction