Structural Dynamics-Us最新文献

In recent years, there has been a major expansion in digital storage capability for hosting raw diffraction datasets. Naturally, the question has now arisen as to the benefits and costs for the preservation of such raw, i.e., experimental diffraction datasets. We describe the consultations made of the global structural chemistry, i.e., chemical crystallography community from the points of view of the International Union of Crystallography (IUCr) Committee on Data, of which JRH was the Chair until very recently, and the IUCrData Raw Data Letters initiative, for which LKB is the Main Editor. The monitoring by the CCDC of CSD depositions which cite the digital object identifiers of raw diffraction datasets provides interesting statistics by probe (x-ray, neutron, or electron) and by home lab vs central facility. Clearly, a better understanding of the reproducibility of current analysis procedures is at hand. Policies for publication requiring raw data have been updated in IUCr Journals for macromolecular crystallography, namely, that raw data should be made available for a new crystal structure or a new method as well as the wwPDB deposition. For chemical crystallography, such a step requiring raw data archiving has not yet been recommended by the IUCr Commission on Structural Chemistry.

Femtosecond optically excited coherent acoustic phonon modes (CAPs) are investigated in a free-standing van der Waals heterostructure composed of a 20-nm transparent hexagonal boron nitride (hBN) and a 42-nm opaque graphite layer. Employing ultrafast electron diffraction, which allows for the independent evaluation of strain dynamics in the constituent material layers, three different CAP modes are identified within the bilayer stack after the optical excitation of the graphite layer. An analytical model is used to discuss the creation of individual CAP modes. Furthermore, their excitation mechanisms in the heterostructure are inferred from the relative phases of these modes by comparison with a numerical linear-chain model. The results support an ultrafast heat transfer mechanism from graphite to the hBN lattice system, which is important to consider when using this material combination in devices.

In this article, we address the application of phase field crystal (PFC) theory, a hybrid atomistic-continuum approach, for modeling nanostructure kinetics encountered in laser deposition. We first provide an overview of the PFC methodology, highlighting recent advances to incorporate phononic and heat transport mechanisms. To simulate laser heating, energy is deposited onto a number of polycrystalline, two-dimensional samples through the application of initial stochastic fluctuations. We first demonstrate the ability of the model to simulate plasticity and recrystallization events that follow laser heating in the isothermal limit. Importantly, we also show that sufficient kinetic energy can cause voiding, which serves to suppress shock propagation. We subsequently employ a newly developed thermo-density PFC theory, coined thermal field crystal (TFC), to investigate laser heating of polycrystalline samples under non-isothermal conditions. We observe that the latent heat of transition associated with ordering can lead to long lasting metastable structures and defects, with a healing rate linked to the thermal diffusion. Finally, we illustrate that the lattice temperature simulated by the TFC model is in qualitative agreement with predictions of conventional electron-phonon two-temperature models. We expect that our new TFC formalism can be useful for predicting transient structures that result from rapid laser heating and re-solidification processes.

The ability to resolve the dynamics of matter on its native temporal and spatial scales constitutes a key challenge and convergent theme across chemistry, biology, and materials science. The last couple of decades have witnessed ultrafast electron diffraction (UED) emerge as one of the forefront techniques with the sensitivity to resolve atomic motions. Increasingly sophisticated UED instruments are being developed that are aimed at increasing the beam brightness in order to observe structural signatures, but so far they have been limited to low average current beams. Here, we present the technical design and capabilities of the HiRES (High Repetition-rate Electron Scattering) instrument, which blends relativistic electrons and high repetition rates to achieve orders of magnitude improvement in average beam current compared to the existing state-of-the-art instruments. The setup utilizes a novel electron source to deliver femtosecond duration electron pulses at up to MHz repetition rates for UED experiments. Instrument response function of sub-500 fs is demonstrated with < 100 fs time resolution targeted in future. We provide example cases of diffraction measurements on solid-state and gas-phase samples, including both micro- and nanodiffraction (featuring 100 nm beam size) modes, which showcase the potential of the instrument for novel UED experiments.

Pump-probe experiments in ultrafast electron microscopy require temporal overlap between the pump and probe pulses. Accurate measurements of the time delay between them allows for the determination of the time zero, the moment in time where both pulses perfectly overlap. In this work, we present the use of a photodiode-based alignment method for these time zero measurements. The cheap and easy-to-use device consists of a photodiode in a sample holder and enables us to temporally align individual, single-electron pulses with femtosecond laser pulses. In a first device, a temporal resolution of 24 ps is obtained, limited by the photodiode design. Future work will utilize a smaller photodiode with a lower capacitance, which will increase the temporal resolution and add spatial resolution as well. This upgrade will bring the method toward the micrometer and picosecond spatiotemporal resolution.

Accurate computations of experimental observables are essential for interpreting the high information content held within x-ray spectra. However, for complicated systems this can be difficult, a challenge compounded when dynamics becomes important owing to the large number of calculations required to capture the time-evolving observable. While machine learning architectures have been shown to represent a promising approach for rapidly predicting spectral lineshapes, achieving simultaneously accurate and sufficiently comprehensive training data is challenging. Herein, we introduce Δ-learning for x-ray spectroscopy. Instead of directly learning the structure-spectrum relationship, the Δ-model learns the structure dependent difference between a higher and lower level of theory. Consequently, once developed these models can be used to translate spectral shapes obtained from lower levels of theory to mimic those corresponding to higher levels of theory. Ultimately, this achieves accurate simulations with a much reduced computational burden as only the lower level of theory is computed, while the model can instantaneously transform this to a spectrum equivalent to a higher level of theory. Our present model, demonstrated herein, learns the difference between TDDFT(BLYP) and TDDFT(B3LYP) spectra. Its effectiveness is illustrated using simulations of Rh L₃-edge spectra tracking the C-H activation of octane by a cyclopentadienyl rhodium carbonyl complex.

The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy, and ab initio molecular dynamics (MD) simulations. The photoluminescence is excited at 4.66 eV, well above the band edge, and shows that electron cooling in the conduction band and exciton formation occur in <500 fs, in excellent agreement with theoretical predictions. The x-ray absorption measurements, obtained upon excitation close to the band edge at 3.49 eV, are sensitive to the migration and trapping of holes. They reveal that the 2 ps transient largely reproduces the previously reported transient obtained at 100 ps time delay in synchrotron studies. In addition, the x-ray absorption signal is found to rise in ∼1.4 ps, which we attribute to the diffusion of holes through the lattice prior to their trapping at singly charged oxygen vacancies. Indeed, the MD simulations show that impulsive trapping of holes induces an ultrafast expansion of the cage of Zn atoms in <200 fs, followed by an oscillatory response at a frequency of ∼100 cm^-1, which corresponds to a phonon mode of the system involving the Zn sub-lattice.

Intense x-ray pulses can cause the non-thermal structural transformation of diamond. At the SACLA XFEL facility, pump x-ray pulses triggered this phase transition, and probe x-ray pulses produced diffraction patterns. Time delays were observed from 0 to 250 fs, and the x-ray dose varied from 0.9 to 8.0 eV/atom. The intensity of the (111), (220), and (311) diffraction peaks decreased with time, indicating a disordering of the crystal lattice. From a Debye-Waller analysis, the rms atomic displacements perpendicular to the (111) planes were observed to be significantly larger than those perpendicular to the (220) or (311) planes. At a long time delay of 33 ms, graphite (002) diffraction indicates that graphitization did occur above a threshold dose of 1.2 eV/atom. These experimental results are in qualitative agreement with XTANT+ simulations using a hybrid model based on density-functional tight-binding molecular dynamics.

We present a dedicated end-station for solution phase high repetition rate (MHz) picosecond hard x-ray spectroscopy at beamline 15-2 of the Stanford Synchrotron Radiation Lightsource. A high-power ultrafast ytterbium-doped fiber laser is used to photoexcite the samples at a repetition rate of 640 kHz, while the data acquisition operates at the 1.28 MHz repetition rate of the storage ring recording data in an alternating on-off mode. The time-resolved x-ray measurements are enabled via gating the x-ray detectors with the 20 mA/70 ps camshaft bunch of SPEAR3, a mode available during the routine operations of the Stanford Synchrotron Radiation Lightsource. As a benchmark study, aiming to demonstrate the advantageous capabilities of this end-station, we have conducted picosecond Fe K-edge x-ray absorption spectroscopy on aqueous [Fe^II(phen)₃]²⁺, a prototypical spin crossover complex that undergoes light-induced excited spin state trapping forming an electronic excited state with a 0.6-0.7 ns lifetime. In addition, we report transient Fe Kβ main line and valence-to-core x-ray emission spectra, showing a unique detection sensitivity and an excellent agreement with model spectra and density functional theory calculations, respectively. Notably, the achieved signal-to-noise ratio, the overall performance, and the routine availability of the developed end-station have enabled a systematic time-resolved science program using the monochromatic beam at the Stanford Synchrotron Radiation Lightsource.