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As with stop-motion photography and flash stroboscopy, in 4D imaging the
molecular motion has to be resolved into frames using a sequence of flashes, in
our case the probing electron pulses. However, 4D electron imaging demands the
marriage of ultrafast probing techniques with those of conventional microscopy
and diffraction, as well as the development of concepts describing the
simultaneous temporal and spatial resolutions of atomic scale. Since the first reports
from this laboratory, the technical and theoretical machinery had to be further
developed, and currently at Caltech there are five table-top instruments for
studies of gases, condensed matter and biological systems. Examples of the
experimental setups for UED, UEC and UEM are displayed below. The conceptual
framework of the approach is as follows. Upon the initiation of the structural
change by either heating of the sample, or through electronic excitation
induced by ultrashort laser pulses, a series of electron pulses is used to
probe the specimen with a well-defined time delay. An electron diffraction
pattern or a micrograph is then obtained. A series of images recorded at a
number of delay times provides a direct insight into the temporal evolution of
the structure. Isolated reactions are studied by using collisionless molecular
beams (UED), while crystals and surfaces are examined either in the reflection
or transmission mode (UEC). For microscopy, the electron beam typically
penetrates a nm-scale sample (UEM). Because electrons strongly
interact with air, the 4D imaging measurements are usually performed in
vacuum.
Central to these approaches is the generation and propagation of
ultrafast coherent electron packets in space and time (see abstracts below). Although the
spatial resolution can reach the atomic scale, imaging must take into
consideration the coherence volume of a single electron and the nature of the
contrast function in the pulsed mode. The temporal resolution is typically
limited by the probing-pulse width and by the difference in group velocities of
electrons and the light used to initiate the dynamical change. With tilted
optical pulses we can now reach limits of time resolution down to regimes of fs
and, possibly, as. The paradigm shift was the realization that imaging can be
achieved using timed and coherent single-electron packets, which are free
of space-charge effects. Images develop in about the same time as that of an
N-electron pulse, but now the time resolution is under control. Increasing the
number of electrons in the pulse can, in principle, result in a single-pulse
imaging, especially suited for irreversible processes that result in permanent
damage. The ever-ongoing research in the areas of laser and electron optics is expected to provide a solid ground for further experimental developments in our laboratory.
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Selected Publications
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Visualizing complexity: Development of 4D
microscopy and diffraction for imaging in space and time, A. H. Zewail, in Visions of Discovery: New Light on Physics, Cosmology and Consciousness, eds. R. Y. Chiao, W. D. Phillips, A. J. Leggett, M. L. Cohen, and C. L. Harper, Jr., Cambridge University Press, Cambridge, 2008. [Web link] [Abstract] [Top of page]
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Ultrashort electron pulses for diffraction,
crystallography and microscopy: Theoretical and experimental resolutions,
A. Gahlmann, S. T. Park, A. H. Zewail, Phys. Chem. Chem. Phys.
2008, 10, 2894-2909. [Web link] [Abstract] [Top of page]
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Attosecond electron pulses for 4D diffraction
and microscopy, P. Baum, A. H. Zewail, Proc. Natl. Acad. Sci. USA
2007, 104, 18409-18414. [Web link] [Abstract] [Top of page]
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Breaking resolution limits in ultrafast
electron diffraction and microscopy, P. Baum, A. H. Zewail, Proc. Natl. Acad. Sci. USA 2006, 103, 16105-16110. [Web link] [Abstract] [Top of page]
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4D ultrafast electron diffraction,
crystallography, and microscopy, A. H. Zewail, Annu. Rev. Phys. Chem. 2006, 57, 65-103. [Web link] [Abstract] [Top of page]
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Diffraction, crystallography, and microscopy
beyond three dimensions: Structural dynamics in space and time,
A. H. Zewail, Phil. Trans. R. Soc. A 2005, 364,
315-329. [Web link] [Abstract]
[See also] [Top of page]
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Chemistry at the uncertainty
limit, A. H. Zewail, Angew. Chem.,
Int. Ed. Engl. 2001, 40, 4371-4375. [Web link] [Abstract] [Top of page]
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Femtosecond transition-state dynamics,
A. H. Zewail, Faraday Discuss. Chem. Soc. 1991, 91,
207-237. [Web link] [Abstract] [Top of page]
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