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  • 1
    Publication Date: 2001-02-13
    Description: 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.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Ihee, H -- Lobastov, V A -- Gomez, U M -- Goodson, B M -- Srinivasan, R -- Ruan, C Y -- Zewail, A H -- New York, N.Y. -- Science. 2001 Jan 19;291(5503):458-62.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Laboratory for Molecular Sciences, Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, CA 91125, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/11161194" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 2
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1988-09-02
    Description: When a chemical bond is broken in a direct dissociation reaction, the process is so rapid that it has generally been considered instantaneous and thus unmeasurable. However, the bond does persist for times on the order of 10(-13) seconds after the photon has been absorbed. Femtosecond (10(-15) second) laser techniques can be used to directly clock this process, which describes the dynamics of the chemical bond. The time required to break the chemical bond in an elementary reaction has been measured and the characteristic repulsion length for the potential governing fragment separation has been obtained.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Rosker, M J -- Dantus, M -- Zewail, A H -- New York, N.Y. -- Science. 1988 Sep 2;241(4870):1200-2.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/17740784" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 3
    Publication Date: 1998-02-18
    Description: The description of chemical reaction dynamics often assumes that vibrational modes are well coupled (ergodic) and redistribute energy rapidly with respect to the course of the reaction. To experimentally probe nonergodic, nonstatistical behavior, studies of a series of reactions induced by femtosecond activation for molecules of varying size but having the same reaction coordinates [CH2 - (CH2)n-2 - C = Odagger --〉 products, with n = 4, 5, 6, and 10] were performed. Comparison of the experimental results with theoretical electronic structure and rate calculations showed a two to four orders of magnitude difference, indicating that the basic assumption of statistical energy redistribution is invalid. These results suggest that chemical selectivity can be achieved with femtosecond activation even at very high energies.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Diau -- Herek -- Kim -- Zewail -- New York, N.Y. -- Science. 1998 Feb 6;279(5352):847-51.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, CA 91125, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/9452381" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 4
    Publication Date: 2009-12-18
    Description: In materials science and biology, optical near-field microscopies enable spatial resolutions beyond the diffraction limit, but they cannot provide the atomic-scale imaging capabilities of electron microscopy. Given the nature of interactions between electrons and photons, and considering their connections through nanostructures, it should be possible to achieve imaging of evanescent electromagnetic fields with electron pulses when such fields are resolved in both space (nanometre and below) and time (femtosecond). Here we report the development of photon-induced near-field electron microscopy (PINEM), and the associated phenomena. We show that the precise spatiotemporal overlap of femtosecond single-electron packets with intense optical pulses at a nanostructure (individual carbon nanotube or silver nanowire in this instance) results in the direct absorption of integer multiples of photon quanta (nhomega) by the relativistic electrons accelerated to 200 keV. By energy-filtering only those electrons resulting from this absorption, it is possible to image directly in space the near-field electric field distribution, obtain the temporal behaviour of the field on the femtosecond timescale, and map its spatial polarization dependence. We believe that the observation of the photon-induced near-field effect in ultrafast electron microscopy demonstrates the potential for many applications, including those of direct space-time imaging of localized fields at interfaces and visualization of phenomena related to photonics, plasmonics and nanostructures.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Barwick, Brett -- Flannigan, David J -- Zewail, Ahmed H -- England -- Nature. 2009 Dec 17;462(7275):902-6. doi: 10.1038/nature08662.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Physical Biology Center for Ultrafast Science and Technology, Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, California 91125, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/20016598" target="_blank"〉PubMed〈/a〉
    Keywords: Electrons ; Lasers ; Metal Nanoparticles/ultrastructure ; Microscopy, Electron/*methods ; Nanotubes, Carbon/radiation effects/ultrastructure ; Nanowires/ultrastructure ; *Photons ; Silver ; Time Factors
    Print ISSN: 0028-0836
    Electronic ISSN: 1476-4687
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
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  • 5
    Publication Date: 2007-11-03
    Description: Complex systems in condensed phases involve a multidimensional energy landscape, and knowledge of transitional structures and separation of time scales for atomic movements is critical to understanding their dynamical behavior. Here, we report, using four-dimensional (4D) femtosecond electron diffraction, the visualization of transitional structures from the initial monoclinic to the final tetragonal phase in crystalline vanadium dioxide; the change was initiated by a near-infrared excitation. By revealing the spatiotemporal behavior from all observed Bragg diffractions in 3D, the femtosecond primary vanadium-vanadium bond dilation, the displacements of atoms in picoseconds, and the sound wave shear motion on hundreds of picoseconds were resolved, elucidating the nature of the structural pathways and the nonconcerted mechanism of the transformation.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Baum, Peter -- Yang, Ding-Shyue -- Zewail, Ahmed H -- New York, N.Y. -- Science. 2007 Nov 2;318(5851):788-92.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Physical Biology Center for Ultrafast Science and Technology, Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, CA 91125, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/17975063" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 6
    Publication Date: 2007-04-21
    Description: Nonequilibrium phase transitions, which are defined by the formation of macroscopic transient domains, are optically dark and cannot be observed through conventional temperature- or pressure-change studies. We have directly determined the structural dynamics of such a nonequilibrium phase transition in a cuprate superconductor. Ultrafast electron crystallography with the use of a tilted optical geometry technique afforded the necessary atomic-scale spatial and temporal resolutions. The observed transient behavior displays a notable "structural isosbestic" point and a threshold effect for the dependence of c-axis expansion (Deltac) on fluence (F), with Deltac/F = 0.02 angstrom/(millijoule per square centimeter). This threshold for photon doping occurs at approximately 0.12 photons per copper site, which is unexpectedly close to the density (per site) of chemically doped carriers needed to induce superconductivity.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Gedik, Nuh -- Yang, Ding-Shyue -- Logvenov, Gennady -- Bozovic, Ivan -- Zewail, Ahmed H -- New York, N.Y. -- Science. 2007 Apr 20;316(5823):425-9.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Physical Biology Center for Ultrafast Science and Technology, California Institute of Technology (Caltech), Pasadena, CA 91125, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/17446397" target="_blank"〉PubMed〈/a〉
    Keywords: Chemistry, Physical ; Copper/*chemistry ; Crystallography/instrumentation/methods ; Electrons ; Lanthanum/*chemistry ; Oxides/*chemistry ; Oxygen/chemistry ; *Phase Transition ; Physicochemical Phenomena
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 7
    Publication Date: 2008-09-20
    Description: The confined electronic structure of nanoscale materials has increasingly been shown to induce behavior quite distinct from that of bulk analogs. Direct atomic-scale visualization of nanowires of zinc oxide was achieved through their unique pancake-type diffraction by using four-dimensional (4D) ultrafast electron crystallography. After electronic excitation of this wide-gap photonic material, the wires were found to exhibit colossal expansions, two orders of magnitude higher than that expected at thermal equilibrium; the expansion is highly anisotropic, a quasi-one-dimensional behavior, and is facilitated by the induced antibonding character. By reducing the density of nanowires, the expansions reach even larger values and occur at shorter times, suggesting a decrease of the structural constraint in transient atomic motions. This unanticipated ultrafast carrier-driven expansion highlights the optoelectronic consequences of nanoscale morphologies.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Yang, Ding-Shyue -- Lao, Changshi -- Zewail, Ahmed H -- New York, N.Y. -- Science. 2008 Sep 19;321(5896):1660-4. doi: 10.1126/science.1162049.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Physical Biology Center for Ultrafast Science and Technology, Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, CA 91125, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/18801993" target="_blank"〉PubMed〈/a〉
    Keywords: Anisotropy ; Crystallography ; Electrons ; Microscopy, Electron, Scanning ; Nanowires/*ultrastructure ; *Zinc Oxide
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 8
    Publication Date: 2009-07-11
    Description: Chemical bonding dynamics are fundamental to the understanding of properties and behavior of materials and molecules. Here, we demonstrate the potential of time-resolved, femtosecond electron energy loss spectroscopy (EELS) for mapping electronic structural changes in the course of nuclear motions. For graphite, it is found that changes of milli-electron volts in the energy range of up to 50 electron volts reveal the compression and expansion of layers on the subpicometer scale (for surface and bulk atoms). These nonequilibrium structural features are correlated with the direction of change from sp2 [two-dimensional (2D) graphene] to sp3 (3D-diamond) electronic hybridization, and the results are compared with theoretical charge-density calculations. The reported femtosecond time resolution of four-dimensional (4D) electron microscopy represents an advance of 10 orders of magnitude over that of conventional EELS methods.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Carbone, Fabrizio -- Kwon, Oh-Hoon -- Zewail, Ahmed H -- New York, N.Y. -- Science. 2009 Jul 10;325(5937):181-4. doi: 10.1126/science.1175005.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Physical Biology Center for Ultrafast Science and Technology, Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, CA 91125, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19589997" target="_blank"〉PubMed〈/a〉
    Keywords: Crystallization ; Graphite/*chemistry ; Lasers ; *Microscopy, Energy-Filtering Transmission Electron ; *Physicochemical Processes ; *Spectroscopy, Electron Energy-Loss
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 9
    Publication Date: 2005-01-08
    Description: The intermediate structures formed through radiationless transitions are termed "dark" because their existence is inferred indirectly from radiative transitions. We used ultrafast electron diffraction to directly determine these transient structures on both ground-state and excited-state potential energy surfaces of several aromatic molecules. The resolution in space and time (0.01 angstrom and 1 picosecond) enables differentiation between competing nonradiative pathways of bond breaking, vibronic coupling, and spin transition. For the systems reported here, the results reveal unexpected dynamical behavior. The observed ring opening of the structure depends on molecular substituents. This, together with the parallel bifurcation into physical and chemical channels, redefines structural dynamics of the energy landscape in radiationless processes.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Srinivasan, Ramesh -- Feenstra, Jonathan S -- Park, Sang Tae -- Xu, Shoujun -- Zewail, Ahmed H -- New York, N.Y. -- Science. 2005 Jan 28;307(5709):558-63. Epub 2005 Jan 6.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Laboratory for Molecular Sciences, Arthur Amos Noyes Laboratory of Chemical Physics, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/15637234" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 10
    Publication Date: 2004-09-18
    Description: We directly observed the hydration dynamics of an excess electron in the finite-sized water clusters of (H2O)n- with n = 15, 20, 25, 30, and 35. We initiated the solvent motion by exciting the hydrated electron in the cluster. By resolving the binding energy of the excess electron in real time with femtosecond resolution, we captured the ultrafast dynamics of the electron in the presolvated ("wet") and hydrated states and obtained, as a function of cluster size, the subsequent relaxation times. The solvation time (300 femtoseconds) after the internal conversion [140 femtoseconds for (H2O)35-] was similar to that of bulk water, indicating the dominant role of the local water structure in the dynamics of hydration. In contrast, the relaxation in other nuclear coordinates was on a much longer time scale (2 to 10 picoseconds) and depended critically on cluster size.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Paik, D Hern -- Lee, I-Ren -- Yang, Ding-Shyue -- Baskin, J Spencer -- Zewail, Ahmed H -- New York, N.Y. -- Science. 2004 Oct 22;306(5696):672-5. Epub 2004 Sep 16.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Arthur Amos Noyes Laboratory of Chemical Physics, Laboratory for Molecular Sciences, California Institute of Technology, Pasadena, CA 91125, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/15375221" target="_blank"〉PubMed〈/a〉
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    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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