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.
Key insights into the behavior of materials can be gained by observing their structure as they undergo lattice distortion. Laser pulses on the femtosecond time scale can be used to induce disorder in ...a "pump-probe" experiment with the ensuing transients being probed stroboscopically with femtosecond pulses of visible light, x-rays, or electrons. Here we report three-dimensional imaging of the generation and subsequent evolution of coherent acoustic phonons on the picosecond time scale within a single gold nanocrystal by means of an x-ray free-electron laser, providing insights into the physics of this phenomenon. Our results allow comparison and confirmation of predictive models based on continuum elasticity theory and molecular dynamics simulations.
Recently, few-femtosecond pulses have become available at hard X-ray free-electron lasers. Coupled with the available sub-10 fs optical pulses, investigations into few-femtosecond dynamics are not ...far off. However, achieving sufficient synchronization between optical lasers and X-ray pulses continues to be challenging. We report a 'measure-and-sort' approach, which achieves sub-10 fs root-mean-squared (r.m.s.) error measurement at hard X-ray FELs, far beyond the 100-200 fs r.m.s. jitter limitations. This timing diagnostic, now routinely available at the Linac Coherent Light Source (LCLS), is based on ultrafast free-carrier generation in optically transparent materials. Correlation between two independent measurements enables unambiguous demonstration of ∼6 fs r.m.s. error in reporting the optical/X-ray delay, with single shot error suggesting the possibility of reaching few-femtosecond resolution.
The resonant excitation of electronic transitions with coherent laser sources creates quantum coherent superpositions of the involved electronic states. Most time-resolved studies have focused on ...gases or isolated subsystems embedded in insulating solids, aiming for applications in quantum information. Here, we focus on the coherent control of orbital wavefunctions in the correlated quantum material Tb2Ti2O7, which forms an interacting spin liquid ground state. We show that resonant excitation with a strong THz pulse creates a coherent superposition of the lowest energy Tb 4f states. The coherence manifests itself as a macroscopic oscillating magnetic dipole, which is detected by ultrafast resonant x-ray diffraction. We envision the coherent control of orbital wavefunctions demonstrated here to become a new tool for the ultrafast manipulation and investigation of quantum materials.Recent years have seen significant progress in the coherent control of collective excitations such as magnons and phonons in quantum materials using ultrafast laser pulses. Here the authors report evidence of coherent excitation of orbitals in a rare earth pyrochlore spin liquid material Tb2Ti2O7 by THz pulses.
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.
Symmetry breaking and the emergence of order is one of the most fascinating phenomena in condensed matter physics. It leads to a plethora of intriguing ground states found in antiferromagnets, Mott ...insulators, superconductors, and density-wave systems. Exploiting states of matter far from equilibrium can provide even more striking routes to symmetry-lowered, ordered states. Here, we demonstrate for the case of elemental chromium that moderate ultrafast photoexcitation can transiently enhance the charge-density-wave (CDW) amplitude by up to 30% above its equilibrium value, while strong excitations lead to an oscillating, large-amplitude CDW state that persists above the equilibrium transition temperature. Both effects result from dynamic electron-phonon interactions, providing an efficient mechanism to selectively transform a broad excitation of the electronic order into a well-defined, long-lived coherent lattice vibration. This mechanism may be exploited to transiently enhance order parameters in other systems with coupled degrees of freedom.
We present a new technique for measuring the relative delay between a soft x-ray FEL pulse and an optical laser that indicates a sub 25 fs RMS measurement error. An ultra-short x-ray pulse ...photo-ionizes a semiconductor (Si(3)N(4)) membrane and changes the optical transmission. An optical continuum pulse with a temporally chirped bandwidth spanning 630 nm-710 nm interacts with the membrane such that the timing of the x-ray pulse can be determined from the onset of the spectral modulation of the transmitted optical pulse. This experiment demonstrates a nearly in situ single-shot measurement of the x-ray pulse arrival time relative to the ultra-short optical pulse.
The objective of this study was to examine the effects of prenatal supplementation and dose of rumen-protected choline (RPC) on neonatal calf growth, metabolism, and vaccine response. Parous Holstein ...cows were blocked by calving month and randomly assigned within block to receive 45 g/d of RPC 20.4 g/d of choline ions (CHOL45), n = 19, 30 g/d of RPC 13.6 g/d of choline ions (CHOL30), n = 22, or no RPC (CON, n = 19) as a top-dress, starting 24 d before expected calving. Calf body weights were recorded for the first 3 wk of life. All calves were fed colostrum replacer (300 g of IgG) at birth, and apparent efficiency of IgG absorption was calculated. On d 1, 7, 14, and 21, blood samples were taken to quantify plasma reactive oxygen and nitrogen species, antioxidant potential, haptoglobin, nonesterified fatty acids (NEFA), β-hydroxybutyrate, and glucose. Calves received an intranasal vaccine at birth, and nasal secretions were collected on d 0, 7, 10, 14, and 21 to quantify bovine respiratory syncytial virus-specific IgA. Data were analyzed using linear mixed models including the fixed effects of treatment, time (when applicable), calf sex, and prepartum dam data (−24 d) along with interactions. Treatment did not affect calf body weight, β-hydroxybutyrate, or glucose concentrations. For apparent efficiency of IgG absorption, treatment interacted with the dam's prepartum body condition score. Where the dam's body condition score was ≤3.25, IgG absorption was reduced in calves born from CHOL45 dams as compared with calves from either CHOL30 or CON dams. Calves from CHOL30 dams had a lesser oxidative stress index (OSi; reactive oxygen and nitrogen species/antioxidant potential) than calves from CON dams. Haptoglobin concentrations were less in heifer calves from CHOL45 dams as compared with heifers from CON dams. The dam's prepartum NEFA concentration interacted with treatment. When dam NEFA was minimal, calves from CHOL45 and CHOL30 dams had greater or tended to have greater NEFA, respectively. Conversely, when dam NEFA was greater, calves from CHOL30 and CHOL45 dams had lesser or tended to have lesser NEFA than calves from CON dams, respectively. For vaccine response, treatment interacted with the dam's prepartum OSi. Among calves born from dams with a greater OSi, calves from CHOL45 and CHOL30 dams had lesser bovine respiratory syncytial virus-specific IgA concentrations in nasal secretions as compared with CON. Prenatal RPC supplementation during late gestation affected IgG absorption, neonatal calf metabolism, and vaccine response with some effects dependent on the dam's prepartum parameters.
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