Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using ...spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.
Time-resolved femtosecond x-ray diffraction patterns from laser-excited molecular iodine are used to create a movie of intramolecular motion with a temporal and spatial resolution of 30 fs and 0.3 Å. ...This high fidelity is due to interference between the nonstationary excitation and the stationary initial charge distribution. The initial state is used as the local oscillator for heterodyne amplification of the excited charge distribution to retrieve real-space movies of atomic motion on ångstrom and femtosecond scales. This x-ray interference has not been employed to image internal motion in molecules before. Coherent vibrational motion and dispersion, dissociation, and rotational dephasing are all clearly visible in the data, thereby demonstrating the stunning sensitivity of heterodyne methods.
We present the first demonstration of THz driven bunch compression and timing stabilization of a relativistic electron beam. Quasi-single-cycle strong field THz radiation is used in a shorted ...parallel-plate structure to compress a few-fC beam with 2.5 MeV kinetic energy by a factor of 2.7, producing a 39 fs rms bunch length and a reduction in timing jitter by more than a factor of 2 to 31 fs rms. This THz driven technique offers a significant improvement to beam performance for applications like ultrafast electron diffraction, providing a critical step towards unprecedented timing resolution in ultrafast sciences, and other accelerator applications using femtosecond-scale electron beams.
Femtosecond pulses from X-ray free-electron lasers offer a powerful method for observing the coherent dynamic of phonons in crystalline materials, it is now shown. This time-resolved spectroscopic ...tool could provide insight into low-energy collective excitations in solids and how they interact at a microscopic level to determine the material's macroscopic properties.
Direct manipulation of the atomic lattice using intense long-wavelength laser pulses has become a viable approach to create new states of matter in complex materials. Conventionally, a high-frequency ...vibrational mode is driven resonantly by a mid-infrared laser pulse and the lattice structure is modified through indirect coupling of this infrared-active phonon to other, lower-frequency lattice modulations. Here, we drive the lowest-frequency optical phonon in the prototypical transition metal oxide SrTiO3 well into the anharmonic regime with an intense terahertz field. We show that it is possible to transfer energy to higher-frequency phonon modes through nonlinear coupling. Our observations are carried out by directly mapping the lattice response to the coherent drive field with femtosecond X-ray pulses, enabling direct visualization of the atomic displacements.A spectroscopic study of strontium titanate provides a method for transferring the vibrational energy of a low-frequency phonon mode to higher-frequency modes, with the potential to access elusive ‘silent’ modes.
We demonstrate single-shot temporal characterization of relativistic electron bunches using single-cycle terahertz (THz) field streaking. A transverse deflecting structure consisting of a metal slit ...enables efficient coupling of the THz field and electron bunch. The intrinsically stable carrier envelope phase and strong gradient of the THz pulses allow simultaneous, self-calibrated determination of the time-of-arrival with subfemtosecond precision and bunch duration with single-femtosecond precision, respectively, opening up new opportunities for ultrafast electron diffraction as well as accelerator technologies in general.
The interactions between electrons and lattice vibrations are fundamental to materials behaviour. In the case of group IV-VI, V and related materials, these interactions are strong, and the materials ...exist near electronic and structural phase transitions. The prototypical example is PbTe whose incipient ferroelectric behaviour has been recently associated with large phonon anharmonicity and thermoelectricity. Here we show that it is primarily electron-phonon coupling involving electron states near the band edges that leads to the ferroelectric instability in PbTe. Using a combination of nonequilibrium lattice dynamics measurements and first principles calculations, we find that photoexcitation reduces the Peierls-like electronic instability and reinforces the paraelectric state. This weakens the long-range forces along the cubic direction tied to resonant bonding and low lattice thermal conductivity. Our results demonstrate how free-electron-laser-based ultrafast X-ray scattering can be utilized to shed light on the microscopic mechanisms that determine materials properties.
The radiolysis of water is ubiquitous in nature and plays a critical role in numerous biochemical and technological applications. Although the elementary reaction pathways for ionized water have been ...studied, the short-lived intermediate complex and structural dynamic response after the proton transfer reaction remain poorly understood. Using a liquid-phase ultrafast electron diffraction technique to measure the intermolecular oxygen···oxygen and oxygen···hydrogen bonds, we captured the short-lived radical-cation complex OH(H
O
) that was formed within 140 femtoseconds through a direct oxygen···oxygen bond contraction and proton transfer, followed by the radical-cation pair dissociation and the subsequent structural relaxation of water within 250 femtoseconds. These measurements provide direct evidence of capturing this metastable radical-cation complex before separation, thereby improving our fundamental understanding of elementary reaction dynamics in ionized liquid water.
Measuring how the magnetic correlations evolve in doped Mott insulators has greatly improved our understanding of the pseudogap, non-Fermi liquids and high-temperature superconductivity. Recently, ...photo-excitation has been used to induce similarly exotic states transiently. However, the lack of available probes of magnetic correlations in the time domain hinders our understanding of these photo-induced states and how they could be controlled. Here, we implement magnetic resonant inelastic X-ray scattering at a free-electron laser to directly determine the magnetic dynamics after photo-doping the Mott insulator Sr2IrO4. We find that the non-equilibrium state, 2 ps after the excitation, exhibits strongly suppressed long-range magnetic order, but hosts photo-carriers that induce strong, non-thermal magnetic correlations. These two-dimensional (2D) in-plane Néel correlations recover within a few picoseconds, whereas the three-dimensional (3D) long-range magnetic order restores on a fluence-dependent timescale of a few hundred picoseconds. The marked difference in these two timescales implies that the dimensionality of magnetic correlations is vital for our understanding of ultrafast magnetic dynamics.
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