Ultrafast Elemental and Oxidation-State Mapping of Hematite by 4D Electron Microscopy.

We describe a new methodology that sheds light on the fundamental electronic processes that occur at the subsurface regions of inorganic solid photocatalysts. Three distinct kinds of microscopic imaging are used that yield spatial, temporal, and energy-resolved information. We also carefully consider the effect of photon-induced near-field electron microscopy (PINEM), first reported by Zewail et al. in 2009. The value of this methodology is illustrated by studying afresh a popular and viable photocatalyst, hematite, α-Fe2O3 that exhibits most of the properties required in a practical application. By employing high-energy electron-loss signals (of several hundred eV), coupled to femtosecond temporal resolution as well as ultrafast energy-filtered transmission electron microscopy in 4D, we have, inter alia, identified Fe4+ ions that have a lifetime of a few picoseconds, as well as associated photoinduced electronic transitions and charge transfer processes.

Entangled nanoparticles: discovery by visualization in 4D electron microscopy.

Particle interactions are fundamental to our understanding of nanomaterials and biological assemblies. Here, we report on the visualization of entangled particles, separated by as large as 70 nm, and the discovery of channels in their near-fields. For silver nanoparticles, the induced field of each particle extends to 50-100 nm, but when particles are brought close in separation we observe channels as narrow as 6 nm, a width that is 2 orders of magnitude smaller than the incident field wavelength. The channels' directions can be controlled by the polarization of the incident field, particle size, and separation. For this direct visualization of these nanoscopic near-fields, the high spatial, temporal, and energy resolutions needed were hitherto not possible without the methodology given here. This methodology, we anticipate, paves the way for further fundamental studies of particle entanglement and for possible applications spanning materials and macromolecular assemblies.

Nanomusical systems visualized and controlled in 4D electron microscopy.

Nanomusical systems, nanoharp and nanopiano, fabricated as arrays of cantilevers by focused ion beam milling of a layered Ni/Ti/Si(3)N(4) thin film, have been investigated in 4D electron microscopy. With the imaging and selective femtosecond and nanosecond control combinations, full characterization of the amplitude and phase of the resonant response of a particular cantilever relative to the optical pulse train was possible. Using a high repetition rate, low energy optical pulse train for selective, resonant excitation, coupled with pulsed and steady-state electron imaging for visualization in space and time, both the amplitude on the nanoscale and resonance of motion on the megahertz scale were resolved for these systems. Tilting of the specimen allowed in-plane and out-of-plane cantilever bending and cantilever torsional motions to be identified in stroboscopic measurements of impulsively induced free vibration. Finally, the transient, as opposed to steady state, thermostat effect was observed for the layered nanocantilevers, with a sufficiently sensitive response to demonstrate suitability for in situ use in thin-film temperature measurements requiring resolutions of <10 K and 10 µm on time scales here mechanically limited to microseconds and potentially at shorter times.

4D Lorentz electron microscopy imaging: magnetic domain wall nucleation, reversal, and wave velocity.

Magnetization reversal is an important topic of research in the fields of both basic and applied ferromagnetism. For the study of magnetization reversal dynamics and magnetic domain wall (DW) motion in ferromagnetic thin films, imaging techniques are indispensable. Here, we report 4D imaging of DWs by the out-of-focus Fresnel method in Lorentz ultrafast electron microscopy (UEM), with in situ spatial and temporal resolutions. The temporal change in magnetization, as revealed by changes in image contrast, is clocked using an impulsive optical field to produce structural deformation of the specimen, thus modulating magnetic field components in the specimen plane. Directly visualized are DW nucleation and subsequent annihilation and oscillatory reappearance (periods of 32 and 45 ns) in nickel films on two different substrates. For the case of Ni films on a Ti/Si(3)N(4) substrate, under conditions of minimum residual external magnetic field, the oscillation is associated with a unique traveling wave train of periodic magnetization reversal. The velocity of DW propagation in this wave train is measured to be 172 m/s with a wavelength of 7.8 microm. The success of this study demonstrates the promise of Lorentz UEM for real-space imaging of spin switching, ferromagnetic resonance, and laser-induced demagnetization in ferromagnetic nanostructures.

Nonchaotic nonlinear motion visualized in complex nanostructures by stereographic 4D electron microscopy.

Direct electron imaging with sufficient time resolution is a powerful tool for visualizing the three-dimensional (3D) mechanical motion and resolving the four-dimensional (4D) trajectories of many different components of a nanomachine, e.g., a NEMS device. Here, we report a nanoscale nonchaotic motion of a nano- and microstructured NiTi shape memory alloy in 4D electron microscopy. A huge amplitude oscillatory mechanical motion following laser heating is observed repetitively, likened to a 3D motion of a conductor's baton. By time-resolved 4D stereographic reconstruction of the motion, prominent vibrational frequencies (3.0, 3.8, 6.8, and 14.5 MHz) are fully characterized, showing evidence of nonlinear behavior. Moreover, it is found that a stress (fluence)--strain (displacement) profile shows nonlinear elasticity. The observed resonances of the nanostructure are reminiscent of classical molecular quasi-periodic behavior, but here both the amplitude and frequency of the motion are visualized using ultrafast electron microscopy.

Direct observation of martensitic phase-transformation dynamics in iron by 4D single-pulse electron microscopy.

The in situ martensitic phase transformation of iron, a complex solid-state transition involving collective atomic displacement and interface movement, is studied in real time by means of four-dimensional (4D) electron microscopy. The iron nanofilm specimen is heated at a maximum rate of approximately 10(11) K/s by a single heating pulse, and the evolution of the phase transformation from body-centered cubic to face-centered cubic crystal structure is followed by means of single-pulse, selected-area diffraction and real-space imaging. Two distinct components are revealed in the evolution of the crystal structure. The first, on the nanosecond time scale, is a direct martensitic transformation, which proceeds in regions heated into the temperature range of stability of the fcc phase, 1185-1667 K. The second, on the microsecond time scale, represents an indirect process for the hottest central zone of laser heating, where the temperature is initially above 1667 K and cooling is the rate-determining step. The mechanism of the direct transformation involves two steps, that of (barrier-crossing) nucleation on the reported nanosecond time scale, followed by a rapid grain growth typically in approximately 100 ps for 10 nm crystallites.

4D ultrafast electron microscopy: imaging of atomic motions, acoustic resonances, and moiré fringe dynamics.

In four-dimensional (4D) ultrafast electron microscopy (UEM), timed-pulse electron imaging and selected-area diffraction are used to study structural dynamics with space- and time-resolutions that allow direct observation of transformations affecting the fundamental properties of materials. Only recently, the UEM studies have begun to reveal a variety of dynamic responses of nanoscale specimens to material excitation, on ultrafast time scales and up to microseconds. Here, we give an account of some of these results, including imaging and diffraction dynamics of gold and graphite single crystal films, revealing atomic motions and morphology change in the former and two forms of acoustic resonance in the latter. We also report, for the first time, dynamic changes upon lattice excitation of moiré fringes in graphite, recorded in bright- and dark-field images. Oscillations that are seen in moiré fringe spacing and other selected-area image properties have the same temporal period as observed in Bragg spot changes in diffraction patterns from the same specimen areas. This period is shown to vary linearly with the local thickness of the specimen, thus establishing that the oscillations are due to excitation of a resonant elastic modulation of the film thickness and allowing derivation of a value of the Young's modulus (c(33)) of 36 GPa for the c-axis strain. The second form of resonance dynamics observed in graphite, on much longer time scales, corresponds to an out-of-plane drumming vibration of the film consistent with a 0.94 TPa elastic modulus for in-plane (a-axis) stretching. For the latter, the nanoscale membrane motion appears complicated ("chaotic") at early time and builds up to a resonance at longer times. Finally, electron energy loss spectroscopy (EELS) in the UEM provides a unique domain of study of chemical bonding on the time scale of change (femtoseconds), and its application to graphite is discussed.

4D imaging of transient structures and morphologies in ultrafast electron microscopy.

With advances in spatial resolution reaching the atomic scale, two-dimensional (2D) and 3D imaging in electron microscopy has become an essential methodology in various fields of study. Here, we report 4D imaging, with in situ spatiotemporal resolutions, in ultrafast electron microscopy (UEM). The ability to capture selected-area-image dynamics with pixel resolution and to control the time separation between pulses for temporal cooling of the specimen made possible studies of fleeting structures and morphologies. We demonstrate the potential for applications with two examples, gold and graphite. For gold, after thermally induced stress, we determined the atomic structural expansion, the nonthermal lattice temperature, and the ultrafast transients of warping/bulging. In contrast, in graphite, striking coherent transients of the structure were observed in both image and diffraction, directly measuring, on the nanoscale, the longitudinal resonance period governed by Young's elastic modulus. The success of these studies demonstrates the promise of UEM in real-space imaging of dynamics.

Nanoscale mechanical drumming visualized by 4D electron microscopy.

With four-dimensional (4D) electron microscopy, we report in situ imaging of the mechanical drumming of a nanoscale material. The single crystal graphite film is found to exhibit global resonance motion that is fully reversible and follows the same evolution after each initiating stress pulse. At early times, the motion appears "chaotic" showing the different mechanical modes present over the micron scale. At longer time, the motion of the thin film collapses into a well-defined fundamental frequency of 1.08 MHz, a behavior reminiscent of mode locking; the mechanical motion damps out after approximately 200 micros and the oscillation has a "cavity" quality factor of 150. The resonance time is determined by the stiffness of the material, and for the 75 nm thick and 40 microm square specimen used here we determined Young's modulus to be 1.0 TPa for the in-plane stress-strain profile. Because of its real-time dimension, this 4D microscopy should have applications in the study of these and other types of materials structures.

4D visualization of embryonic, structural crystallization by single-pulse microscopy.

In many physical and biological systems the transition from an amorphous to ordered native structure involves complex energy landscapes, and understanding such transformations requires not only their thermodynamics but also the structural dynamics during the process. Here, we extend our 4D visualization method with electron imaging to include the study of irreversible processes with a single pulse in the same ultrafast electron microscope (UEM) as used before in the single-electron mode for the study of reversible processes. With this augmentation, we report on the transformation of amorphous to crystalline structure with silicon as an example. A single heating pulse was used to initiate crystallization from the amorphous phase while a single packet of electrons imaged selectively in space the transformation as the structure continuously changes with time. From the evolution of crystallinity in real time and the changes in morphology, for nanosecond and femtosecond pulse heating, we describe two types of processes, one that occurs at early time and involves a nondiffusive motion and another that takes place on a longer time scale. Similar mechanisms of two distinct time scales may perhaps be important in biomolecular folding.

Atomic-scale imaging in real and energy space developed in ultrafast electron microscopy.

In this contribution, we report the development of ultrafast electron microscopy (UEM) with atomic-scale real-, energy-, and Fourier-space resolutions. This second-generation UEM provides images, diffraction patterns, and electron energy spectra, and here we demonstrate its potential with applications for nanostructured materials and organometallic crystals. We clearly resolve the separation between atoms in the direct images and the Bragg spots/Debye-Scherrer rings in diffraction and obtain the electronic structure and elemental energies in the electron energy loss spectra (EELS) and energy filtered transmission electron microscopy (EFTEM).

Ultrafast vectorial and scalar dynamics of ionic clusters: azobenzene solvated by oxygen.

The ultrafast dynamics of clusters of trans-azobenzene anion (A-) solvated by oxygen molecules was investigated using femtosecond time-resolved photoelectron spectroscopy. The time scale for stripping off all oxygen molecules from A- was determined by monitoring in real time the transient of the A- rise, following an 800 nm excitation of A- (O2)n, where n = 1-4. A careful analysis of the time-dependent photoelectron spectra strongly suggests that for n > 1 a quasi-O4 core is formed and that the dissociation occurs by a bond cleavage between A- and conglomerated (O2)n rather than a stepwise evaporation of O2. With time and energy resolutions, we were able to capture the photoelectron signatures of transient species which instantaneously rise (<100 fs) then decay. The transient species are assigned as charge-transfer complexes: A.O2- for A- O2 and A.O4-(O2)n-2 for A-(O2)n, where n = 2-4. Subsequent to an ultrafast electron recombination, A- rises with two distinct time scales: a subpicosecond component reflecting a direct bond rupture of the A- -(O2)n nuclear coordinate and a slower component (1.6-36 ps, increasing with n) attributed to an indirect channel exhibiting a quasistatistical behavior. The photodetachment transients exhibit a change in the transition dipole direction as a function of time delay. Rotational dephasing occurs on a time scale of 2-3 ps, with a change in the sign of the transient anisotropy between A- O2 and the larger clusters. This behavior is a key indicator of an evolving cluster structure and is successfully modeled by calculations based on the structures and inertial motion of the parent clusters.

Oriented ensembles in ultrafast electron diffraction.

Electron scattering expressions are presented which are applicable to very general conditions of implementation of anisotropic ultrafast electron diffraction (UED) experiments on the femto- and picosecond time scale. "Magic angle" methods for extracting from the experimental diffraction patterns both the isotropic scalar contribution (population dynamics) and the angular (orientation-dependent) contribution are described. To achieve this result, the molecular scattering intensity is given as an expansion in terms of the moments of the transition-dipole distribution created by the linearly polarized excitation laser pulse. The isotropic component (n=0 moment) depends only on population and scalar internuclear separations, and the higher moments reflect bond angles and evolve in time due to rotational motion of the molecules. This clear analytical separation facilitates assessment of the role of experimental variables in determining the influence of anisotropic orientational distributions of the molecular ensembles on the measured diffraction patterns. Practical procedures to separate the isotropic and anisotropic components of experimental data are evaluated and demonstrated with application to reactions. The influence of vectorial properties (bond angles and rotational dynamics) on the anisotropic component adds a new dimension to UED, arising through the imposition of spatial order on otherwise randomly oriented ensembles.

Dynamics of clusters: from elementary to biological structures.

Between isolated atoms or molecules and bulk materials there lies a class of unique structures, known as clusters, that consist of a few to hundreds of atoms or molecules. Within this range of "nanophase," many physical and chemical properties of the materials evolve as a function of cluster size, and materials may exhibit novel properties due to quantum confinement effects. Understanding these phenomena is in its own rights fundamental, but clusters have the additional advantage of being controllable model systems for unraveling the complexity of condensed-phase and biological structures, not to mention their vanguard role in defining nanoscience and nanotechnology. Over the last two decades, much progress has been made, and this short overview highlights our own involvement in developing cluster dynamics, from the first experiments on elementary systems to model systems in the condensed phase, and on to biological structures.

Ultrafast electron diffraction: oriented molecular structures in space and time.

The technique of ultrafast electron diffraction allows direct measurement of changes which occur in the molecular structures of isolated molecules upon excitation by femtosecond laser pulses. The vectorial nature of the molecule-radiation interaction also ensures that the orientation of the transient populations created by the laser excitation is not isotropic. Here, we examine the influence on electron diffraction measurements--on the femtosecond and picosecond timescales--of this induced initial anisotropy and subsequent inertial (collision-free) molecular reorientation, accounting for the geometry and dynamics of a laser-induced reaction (dissociation). The orientations of both the residual ground-state population and the excited- or product-state populations evolve in time, with different characteristic rotational dephasing and recurrence times due to differing moments of inertia. This purely orientational evolution imposes a corresponding evolution on the electron scattering pattern, which we show may be similar to evolution due to intrinsic structural changes in the molecule, and thus potentially subject to misinterpretation. The contribution of each internuclear separation is shown to depend on its orientation in the molecular frame relative to the transition dipole for the photoexcitation; thus not only bond lengths, but also bond angles leave a characteristic imprint on the diffraction. Of particular note is the fact that the influence of anisotropy persists at all times, producing distinct differences between the asymptotic "static" diffraction image and the predictions of isotropic diffraction theory.

Human myoglobin recognition of oxygen: dynamics of the energy landscape.

Femtosecond to nanosecond dynamics of O(2) rebinding to human WT myoglobin and its mutants, V68F and I107F, have been studied by using transient absorption. The results are compared with NO rebinding. Even though the immediate environment around the heme binding site is changed by the mutations, the picosecond geminate rebinding of oxygen is at most minimally affected. On the other hand, the V68F (E11) mutation causes drastic differences in rebinding on the nanosecond time scale, whereas the effect of the I107F (G8) mutation remains relatively small within our 10-ns time window. Unlike traditional homogeneous kinetics and molecular dynamics collisional simulations, we propose a "bifurcation model" for populations of directed and undirected dynamics on the ultrafast time scale, reflecting the distribution of initial protein conformations. The major mutation effect occurs on the time scale on which global protein conformational change is possible, consistent with transitions between the conformations of directed and undirected population playing a role in the O(2) binding. We discuss the relevance of these findings to the bimolecular function of the protein.

Electrons in finite-sized water cavities: hydration dynamics observed in real time.

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.

Molecular recognition of oxygen by protein mimics: dynamics on the femtosecond to microsecond time scale.

Molecular recognition by biological macromolecules involves many elementary steps, usually convoluted by diffusion processes. Here we report studies of the dynamics, from the femtosecond to the microsecond time scale, of the different elementary processes involved in the bimolecular recognition of a protein mimic, cobalt picket-fence porphyrin, with varying oxygen concentration at controlled temperatures. Electron transfer, bond breakage, and thermal "on" (recombination) and "off" (dissociation) reactions are the different processes involved. The reaction on-rate is 30 to 60 times smaller than that calculated from standard Smoluchowski theory. Introducing a two-step recognition model, with reversibility being part of both steps, removes the discrepancy and provides consistency for the reported thermodynamics, kinetics, and dynamics. The transient intermediates are configurations defined by the contact between oxygen (diatomic) and the picket-fence porphyrin (macromolecule). This intermediate is critical in the description of the potential energy landscape but, as shown here, both enthalpic and entropic contributions to the free energy are important. In the recognition process, the net entropy decrease is -33 cal mol(-1) K(-1); Delta H is -13.4 kcal mol(-1).