Project description:Water is ubiquitous on earth, but we know little about the real-space motion of molecules in liquid water. We demonstrate that high-resolution inelastic x-ray scattering measurement over a wide range of momentum and energy transfer makes it possible to probe real-space, real-time dynamics of water molecules through the so-called Van Hove function. Water molecules are found to be strongly correlated in space and time with coupling between the first and second nearest-neighbor molecules. The local dynamic correlation of molecules observed here is crucial to a fundamental understanding of the origin of the physical properties of water, including viscosity. The results also suggest that the quantum-mechanical nature of hydrogen bonds could influence its dynamics. The approach used here offers a powerful experimental method for investigating real-space dynamics of liquids.
Project description:Multi-slice simulations of electron diffraction by three-dimensional protein crystals have indicated that structure solution would be severely impeded by dynamical diffraction, especially when crystals are more than a few unit cells thick. In practice, however, dynamical diffraction turned out to be less of a problem than anticipated on the basis of these simulations. Here it is shown that two scattering phenomena, which are usually omitted from multi-slice simulations, reduce the dynamical effect: solvent scattering reduces the phase differences within the exit beam and inelastic scattering followed by elastic scattering results in diffusion of dynamical scattering out of Bragg peaks. Thus, these independent phenomena provide potential reasons for the apparent discrepancy between theory and practice in protein electron crystallography.
Project description:Inelastic Neutron Scattering (INS) spectroscopy has provided a unique insight into the magnetodymanics of nanoscale copper (II) oxide (CuO). We present evidence for the propagation of magnons in the directions of the ordering vectors of both the commensurate and helically modulated incommensurate antiferromagnetic phases of CuO. The temperature dependency of the magnon spin-wave intensity (in the accessible energy-range of the experiment) conforms to the Bose population of states at low temperatures (T ≤ 100 K), as expected for bosons, then intensity significantly increases, with maximum at about 225 K (close to TN), and decreases at higher temperatures. The obtained results can be related to gradual softening of the dispersion curves of magnon spin-waves and decreasing the spin gap with temperature approaching TN on heating, and slow dissipation of the short-range dynamic spin correlations at higher temperatures. However, the intensity of the magnon signal was found to be particle size dependent, and increases with decreasing particle size. This "reverse size effect" is believed to be related to either creation of single-domain particles at the nanoscale, or "superferromagnetism effect" and the formation of collective particle states.
Project description:Inelastic neutron scattering (INS) provides a weighted density of phonon modes. Currently, INS spectra can only be interpreted for perfectly crystalline materials because of high computational cost for electronic simulations. INS has the potential to provide detailed morphological information if sufficiently large volumes and appropriate structural variety are simulated. Here, we propose a method that allows direct comparison between INS data with molecular dynamics simulations, a simulation method that is frequently used to simulate semicrystalline/amorphous materials. We illustrate the technique by analyzing spectra of a well-studied conjugated polymer, poly(3-hexylthiophene-2,5-diyl) (P3HT) and conclude that our technique provides improved volume and structural variety, but that the classical force field requires improvement before the morphology can be accurately interpreted.
Project description:As a contribution to the ongoing effort toward high-frequency sound manipulation in composite materials, we use Inelastic X-ray Scattering to probe the phonon spectrum of ice, either in a pure form or with a sparse amount of nanoparticles embedded in it. The study aims at elucidating the ability of nanocolloids to condition the collective atomic vibrations of the surrounding environment. We observe that a nanoparticle concentration of about 1 % in volume is sufficient to visibly affect the phonon spectrum of the icy substrate, mainly canceling its optical modes and adding nanoparticle phonon excitations to it. We highlight this phenomenon thanks to the lineshape modeling based on a Bayesian inference, which enables us to capture the finest detail of the scattering signal. The results of this study can empower new routes toward the shaping of sound propagation in materials through the control of their structural heterogeneity.
Project description:A new approach to the interpretation and analysis of coherent inelastic neutron scattering from polycrystals (poly-CINS) is presented. This article describes a simulation of the one-phonon coherent inelastic scattering from a lattice model of an arbitrary crystal system. The one-phonon component is characterized by sharp features, determined, for example, by boundaries of the (Q, ?) regions where one-phonon scattering is allowed. These features may be identified with the same features apparent in the measured total coherent inelastic cross section, the other components of which (multiphonon or multiple scattering) show no sharp features. The parameters of the model can then be relaxed to improve the fit between model and experiment. This method is of particular interest where no single crystals are available. To test the approach, the poly-CINS has been measured for polycrystalline aluminium using the MARI spectrometer (ISIS), because both lattice dynamical models and measured dispersion curves are available for this material. The models used include a simple Lennard-Jones model fitted to the elastic constants of this material plus a number of embedded atom method force fields. The agreement obtained suggests that the method demonstrated should be effective in developing models for other materials where single-crystal dispersion curves are not available.
Project description:The control and detection of crystallographic chirality is an important and challenging scientific problem. Chirality has wide ranging implications from medical physics to cosmology including an intimate but subtle connection in magnetic systems, for example Mn1-xFexSi. X-ray diffraction techniques with resonant or polarized variations of the experimental setup are currently utilized to characterize lattice chirality. We demonstrate using theoretical calculations the feasibility of indirect K -edge bimagnon resonant inelastic X-ray scattering (RIXS) spectrum as a viable experimental technique to distinguish crystallographic handedness. We apply spin wave theory to the recently discovered √5 × √5 vacancy ordered chalcogenide Rb0.89Fe1.58Se2 for realistic X-ray experimental set up parameters (incoming energy, polarization, Bragg angle, and experimental resolution) to show that the computed RIXS spectrum is sensitive to the underlying handedness (right or left) of the lattice. A Flack parameter definition that incorporates the right- and left- chiral lattice RIXS response is introduced. It is shown that the RIXS response of the multiband magnon system RbFeSe arises both from inter- and intra- band scattering processes. The extinction or survival of these RIXS peaks are sensitive to the underlying chiral lattice orientation. This in turn allows for the identification of the two chiral lattice orientations.
Project description:Entanglement is a crucial resource for quantum information processing and its detection and quantification is of paramount importance in many areas of current research. Weakly coupled molecular nanomagnets provide an ideal test bed for investigating entanglement between complex spin systems. However, entanglement in these systems has only been experimentally demonstrated rather indirectly by macroscopic techniques or by fitting trial model Hamiltonians to experimental data. Here we show that four-dimensional inelastic neutron scattering enables us to portray entanglement in weakly coupled molecular qubits and to quantify it. We exploit a prototype (Cr7Ni)2 supramolecular dimer as a benchmark to demonstrate the potential of this approach, which allows one to extract the concurrence in eigenstates of a dimer of molecular qubits without diagonalizing its full Hamiltonian.
Project description:Structural transition in amorphous oxides, including glasses, under extreme compression above megabar pressures (>1 million atmospheric pressure, 100 GPa) results in unique densification paths that differ from those in crystals. Experimentally verifying the atomistic origins of such densifications beyond 100 GPa remains unknown. Progress in inelastic X-ray scattering (IXS) provided insights into the pressure-induced bonding changes in oxide glasses; however, IXS has a signal intensity several orders of magnitude smaller than that of elastic X-rays, posing challenges for probing glass structures above 100 GPa near the Earth's core-mantle boundary. Here, we report megabar IXS spectra for prototypical B2O3 glasses at high pressure up to ?120 GPa, where it is found that only four-coordinated boron ([4]B) is prevalent. The reduction in the [4]B-O length up to 120 GPa is minor, indicating the extended stability of sp3-bonded [4]B. In contrast, a substantial decrease in the average O-O distance upon compression is revealed, suggesting that the densification in B2O3 glasses is primarily due to O-O distance reduction without the formation of [5]B. Together with earlier results with other archetypal oxide glasses, such as SiO2 and GeO2, the current results confirm that the transition pressure of the formation of highly coordinated framework cations systematically increases with the decreasing atomic radius of the cations. These observations highlight a new opportunity to study the structure of oxide glass above megabar pressures, yielding the atomistic origins of densification in melts at the Earth's core-mantle boundary.
Project description:Tautomerism is one of the most important forms of isomerism, owing to the facile interconversion between species and the large differences in chemical properties introduced by the proton transfer connecting the tautomers. Spectroscopic techniques are often used for the characterization of tautomers. In this context, separating the overlapping spectral response of coexisting tautomers is a long-standing challenge in chemistry. Here, we demonstrate that by using resonant inelastic X-ray scattering tuned to the core excited states at the site of proton exchange between tautomers one is able to experimentally disentangle the manifold of valence excited states of each tautomer in a mixture. The technique is applied to the prototypical keto-enol equilibrium of 3-hydroxypyridine in aqueous solution. We detect transitions from the occupied orbitals into the LUMO for each tautomer in solution, which report on intrinsic and hydrogen-bond-induced orbital polarization within the π and σ manifolds at the proton-transfer site.