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Ultrafast Electron Diffraction (UED) with atomic-scale, combined spatial and
temporal resolution is a powerful tool for determination of structural
dynamics. In order to spatially resolve a molecular structure, the
wavelength required is sub-Å, which can be easily obtained using
accelerated electrons: λde Broglie = 0.067 Å at 30
keV. The atoms in a specimen act as scattering centers for incident
electrons, and each atom becomes a coherent source of an outgoing spherical
wave. The electron diffraction experiment thus becomes a conceptual analog
of the well-known multi-slit diffraction experiment, but at the molecular
length scale. That is why electron diffraction is often used to
elucidate the three-dimensional architecture of isolated molecules, amorphous
materials, and (thin) crystals.
Because of
the very large cross-section for scattering of electrons, as compared to that
of X-ray light, it is possible to achive the ultrafast time resolution when
studying molecular systems in the gas phase (a nontrivial task because of the
lack of long-range order and low molecular density). The UED approach developed at
Caltech has been successfully used to study chemical reactions, excited-sate
structure dynamics, and nonequilibrium conformational changes on their native ultrafast time
scales (see abstracts below). With UED, dark transient structures unobservable by spectroscopic
methods can be determined and visualized. Ongoing UED research involves
studies of complex chemical structures and biological chromophores. The
construction of a fourth-generation instrument capable of investigating
biomolecules in the gas phase is a significant part in this effort. The goal
is to reveal, in the absence of a perturbing solvent, the intrinsic structural
dynamics of the species, in the hope of identifying degrees of
freedom critical to the understanding of their biological functionality.
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Selected Publications
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Structure of isolated biomolecules by electron diffraction — laser desorption: Uracil and guanine,
A. Gahlmann, S. T. Park, A. H. Zewail, J. Am. Chem. Soc. 2009, 131, 2806-2808. [Web link] [Abstract] [Top of page]
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Ultrafast electron diffraction: Structural
dynamics of molecular rearrangement in the NO release from nitrobenzene,
Y. He, A. Gahlmann, J. S. Feenstra, S. T. Park, A. H. Zewail, Chem.-Asian
J. 2006, 1, 56-63. [Web link] [Abstract] [Top of page]
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Ultrafast electron diffraction: Excited
state structures and chemistries of aromatic carbonyls, S. T. Park,
J. S. Feenstra, A. H. Zewail, J. Chem. Phys. 2006, 124,
174707. [Web link] [Abstract] [Top of page]
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Dark structures in molecular radiationless transitions determined by ultrafast diffraction, R. Srinivasan,
J. S. Feenstra, S. T. Park, S. Xu, A. H. Zewail, Science 2005,
307, 558-563. [Web link] [Abstract] [Top of page]
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Ultrafast electron diffraction (UED): A new
development for the 4D determination of transient molecular structures,
R. Srinivasan, V. A. Lobastov, C.-Y. Ruan, A. H. Zewail,
Helv. Chim. Acta 2003, 86, 1763-1838. [Web link] [Abstract] [Top of page]
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Ultrafast diffraction of transient molecular
structures in radiationless transitions, V. A. Lobastov, R. Srinivasan,
B. M. Goodson, C.-Y. Ruan, J. S. Feenstra, A. H. Zewail,
J. Phys. Chem. A 2001, 105, 11159-11164. [Web link] [Abstract] [Top of page]
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Direct imaging of transient molecular
structures with ultrafast diffraction, H. Ihee, V. A. Lobastov, U. Gomez,
B. M. Goodson, R. Srinivasan, C.-Y. Ruan, A. H. Zewail, Science
2001, 291, 458-462. [Web link] [Abstract] [Top of page]
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