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

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 μm. 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

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 (2- 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

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

Picosecond real-time studies of mode-specific vibrational predissociation

The vibrational predissociation of several van der Waals complexes of t-stilbene has been studied by directly measuring, in real time, the fluorescence intensity from the initial reactant state and from the individual product states formed in the dissociation process after exciting single vibrational levels of the complex. With the aid of a kinetic model involving sequential processes, the individual rates for intramolecular vibrational redistribution and vibrational predissociation in the overall dissociation process are resolved and distinguished in several cases. In the stilbene–He complex, the dissociation is significantly faster from low energy out-of-plane modes than it is from a higher energy in-plane mode

Ultrafast elemental and oxidation-state mapping of hematite by 4D electron microscopy

This work was supported by the Air Force Office of Scientific Research (FA9550-11-1-0055) in the Gordon and Betty Moore Center for Physical Biology at the California Institute of Technology.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.PostprintPeer reviewe

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)

Purely rotational coherence effect and time-resolved sub-Doppler spectroscopy of large molecules. II. Experimental

In this paper we describe the results of picosecond fluorescence polarization (sub-Doppler) experiments designed to determine the role of purely rotational coherence in two jet-cooled molecules: trans-stilbene and anthracene. Observations of the manifestations of purely rotational coherence in t-stilbene are reported. The relationship of purely rotational coherence to molecular parameters (excited state rotational constants and transition dipole directions) is confirmed by comparison of our measurements with the results of the theory described in paper I [P. M. Felker and A. H. Zewail, J. Chem. Phys. 86, 2460 (1987)]. The sum of rotational constants B[script '] and C[script '] of the t-stilbene S1 electronic state is determined with a precision of better than 1 part in 700 (B[script ']+C[script ']=0.5132±0.0007 GHz). The influence of molecular beam expansion conditions and fluorescence detection conditions on our measurements is also investigated and compared with the theroretical findings of paper I. Also measurements of time-resolved and polarization-analyzed fluorescence as a function of excess vibrational energy in the S1 electronic states of both t-stilbene and anthracene are reported. We are able to distinguish the contribution of purely rotational coherence from the contributions of purely vibrational (or rovibrational) coherence to the evolution of fluorescence from the vibrationally excited molecule. The results are first analyzed on the basis of a model in which strict separability of vibrational and rotational motion is assumed. This provides a test of the extent of coupling of these motions and its influence on intramolecular vibrational energy redistribution (IVR)

Picosecond IVR dynamics of p-difluorobenzene and p-fluorotoluene in a molecular beam: Comparison with chemical timing data

We present in this Communication preliminary time-resolved fluorescence measurements of supersonaically cooled samples of pDFB and pFT. These measurements indicate that IVR in both cold molecules up to ~1600 cm^-1 of excess vibrational energy is substantially less than that reported for the same vibrational excitations in room temperature chemical timing studies