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.
Terahertz-frequency optical pulses can resonantly drive selected vibrational modes in solids and deform their crystal structures. In complex oxides, this method has been used to melt electronic ...order, drive insulator-to-metal transitions and induce superconductivity. Strikingly, coherent interlayer transport strongly reminiscent of superconductivity can be transiently induced up to room temperature (300 kelvin) in YBa2Cu3O6+x (refs 9, 10). Here we report the crystal structure of this exotic non-equilibrium state, determined by femtosecond X-ray diffraction and ab initio density functional theory calculations. We find that nonlinear lattice excitation in normal-state YBa2Cu3O6+x at above the transition temperature of 52 kelvin causes a simultaneous increase and decrease in the Cu-O2 intra-bilayer and, respectively, inter-bilayer distances, accompanied by anisotropic changes in the in-plane O-Cu-O bond buckling. Density functional theory calculations indicate that these motions cause drastic changes in the electronic structure. Among these, the enhancement in the character of the in-plane electronic structure is likely to favour superconductivity.
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.
An era of exploring the interactions of high-intensity, hard X-rays with matter has begun with the start-up of a hard-X-ray free-electron laser, the Linac Coherent Light Source (LCLS). Understanding ...how electrons in matter respond to ultra-intense X-ray radiation is essential for all applications. Here we reveal the nature of the electronic response in a free atom to unprecedented high-intensity, short-wavelength, high-fluence radiation (respectively 10(18) W cm(-2), 1.5-0.6 nm, approximately 10(5) X-ray photons per A(2)). At this fluence, the neon target inevitably changes during the course of a single femtosecond-duration X-ray pulse-by sequentially ejecting electrons-to produce fully-stripped neon through absorption of six photons. Rapid photoejection of inner-shell electrons produces 'hollow' atoms and an intensity-induced X-ray transparency. Such transparency, due to the presence of inner-shell vacancies, can be induced in all atomic, molecular and condensed matter systems at high intensity. Quantitative comparison with theory allows us to extract LCLS fluence and pulse duration. Our successful modelling of X-ray/atom interactions using a straightforward rate equation approach augurs favourably for extension to complex systems.
The Einstein-de Haas effect was originally observed in a landmark experiment
demonstrating that the angular momentum associated with aligned electron spins in a ferromagnet can be converted to ...mechanical angular momentum by reversing the direction of magnetization using an external magnetic field. A related problem concerns the timescale of this angular momentum transfer. Experiments have established that intense photoexcitation in several metallic ferromagnets leads to a drop in magnetization on a timescale shorter than 100 femtoseconds-a phenomenon called ultrafast demagnetization
. Although the microscopic mechanism for this process has been hotly debated, the key question of where the angular momentum goes on these femtosecond timescales remains unanswered. Here we use femtosecond time-resolved X-ray diffraction to show that most of the angular momentum lost from the spin system upon laser-induced demagnetization of ferromagnetic iron is transferred to the lattice on sub-picosecond timescales, launching a transverse strain wave that propagates from the surface into the bulk. By fitting a simple model of the X-ray data to simulations and optical data, we estimate that the angular momentum transfer occurs on a timescale of 200 femtoseconds and corresponds to 80 per cent of the angular momentum that is lost from the spin system. Our results show that interaction with the lattice has an essential role in the process of ultrafast demagnetization in this system.
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 employ time-resolved resonant x-ray diffraction to study the melting of charge order and the associated insulator-to-metal transition in the doped manganite Pr_{0.5}Ca_{0.5}MnO_{3} after resonant ...excitation of a high-frequency infrared-active lattice mode. We find that the charge order reduces promptly and highly nonlinearly as function of excitation fluence. Density-functional theory calculations suggest that direct anharmonic coupling between the excited lattice mode and the electronic structure drives these dynamics, highlighting a new avenue of nonlinear phonon control.
Selective optical excitation of a substrate lattice can drive phase changes across heterointerfaces. This phenomenon is a nonequilibrium analogue of static strain control in heterostructures and may ...lead to new applications in optically controlled phase change devices. Here, we make use of time-resolved nonresonant and resonant x-ray diffraction to clarify the underlying physics and to separate different microscopic degrees of freedom in space and time. We measure the dynamics of the lattice and that of the charge disproportionation in NdNiO_{3}, when an insulator-metal transition is driven by coherent lattice distortions in the LaAlO_{3} substrate. We find that charge redistribution propagates at supersonic speeds from the interface into the NdNiO_{3} film, followed by a sonic lattice wave. When combined with measurements of magnetic disordering and of the metal-insulator transition, these results establish a hierarchy of events for ultrafast control at complex-oxide heterointerfaces.
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.
Strongly correlated electron systems often exhibit very strong interactions between structural and electronic degrees of freedom that lead to complex and interesting phase diagrams. For technological ...applications of these materials it is important to learn how to drive transitions from one phase to another. A key question here is the ultimate speed of such phase transitions, and to understand how a phase transition evolves in the time domain. Here we apply time-resolved X-ray diffraction to directly measure the changes in long-range order during ultrafast melting of the charge and orbitally ordered phase in a perovskite manganite. We find that although the actual change in crystal symmetry associated with this transition occurs over different timescales characteristic of the many electronic and vibrational coordinates of the system, the dynamics of the phase transformation can be well described using a single time-dependent 'order parameter' that depends exclusively on the electronic excitation.
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