Analysis Of Quasielastic Neutron Scattering Data Research Articles

Influence of the Halide Ion on the A-Site Dynamics in FAPbX3 (X = Br and Cl)

The optoelectronic properties and ultimately photovoltaic performance of hybrid lead halide perovskites are inherently related to the dynamics of the organic cations. Here, we report the dynamics of the formamidinium (FA) cation in FAPbX3 perovskites for chloride and bromide varieties, as studied by neutron spectroscopy. Elastic fixed window scans showed the onset of the reorientational motion of FA cations in FAPbCl3 to occur at a considerably higher temperature compared to that in FAPbBr3. In addition, we observed two distinct dynamical transitions only in the chloride system, suggesting a significant variation in the reorientational motions of the FA cation with temperature. Quasielastic neutron scattering data analysis of FAPbCl3 showed that in the low-temperature orthorhombic phase, FA cations undergo twofold jump reorientations about the C–H axis, which evolve into an isotropic rotation in the intermediate tetragonal and high-temperature cubic phases. Comparing the results with those from FAPbBr3 reveals that the time scale and barrier to reorientation and the geometry of the reorientational motion of the FA cations are significantly different for the two halides. We note that this dependence of the dynamic properties of the A-site cation on the halide is unique to the FA series; the geometry of methylammonium (MA) cation dynamics in MAPbX3 is known to be insensitive to different halides.

Temperature-dependent dynamic structure factors for liquid water inferred from inelastic neutron scattering measurements.

Temperature-dependent dynamic structure factors S(Q, ω) for liquid water have been calculated using a composite model, which is based on the decoupling approximation of the mean square displacement of the water molecules into diffusion and solid-like vibrational parts. The solid-like vibrational part Svib(Q, ω) is calculated with the phonon expansion method established in the framework of the incoherent Gaussian approximation. The diffusion part Sdiff(Q, ω) relies on the Egelstaff-Schofield translational diffusion model corrected for jump diffusions and rotational diffusions with the Singwi-Sjölander random model and Sears expansion, respectively. Systematics of the model parameters as a function of temperature were deduced from quasi-elastic neutron scattering data analysis reported in the literature and from molecular dynamics (MD) simulations relying on the TIP4P/2005f model. The resulting S(Q, ω) values are confronted by means of Monte Carlo simulations to inelastic neutron scattering data measured with IN4, IN5, and IN6 time-of-flight spectrometers of the Institut Laue-Langevin (ILL) (Grenoble, France). A modest range of temperatures (283-494K) has been investigated with neutron wavelengths corresponding to incident neutron energies ranging from 0.57 to 67.6 meV. The neutron-weighted multiphonon spectra deduced from the ILL data indicate a slight overestimation by the MD simulations of the frequency shift and broadening of the librational band. The descriptive power of the composite model was suited for improving the comparison to experiments via Bayesian updating of prior model parameters inferred from MD simulations. The reported posterior temperature-dependent densities of state of hydrogen in H2O would represent valuable insights for studying the collective coupling interactions in the water molecule between the inter- and intramolecular degrees of freedom.

Mode-distribution analysis of quasielastic neutron scattering and application to liquid water

A quasielastic neutron scattering (QENS) experiment is a particular technique that endeavors to define a relationship between time and space for the diffusion dynamics of atoms and molecules. However, in most cases, analyses of QENS data are model dependent, which may distort attempts to elucidate the actual diffusion dynamics. We have developed a method for processing QENS data without a specific model, wherein all modes can be described as combinations of the relaxations based on the exponential law. By this method, we can obtain a distribution function B(Q,Γ), which we call the mode-distribution function (MDF), to represent the number of relaxation modes and distributions of the relaxation times in the modes. The deduction of MDF is based on the maximum entropy method and is very versatile in QENS data analysis. To verify this method, reproducibility was checked against several analytical models, such as that with a mode of distributed relaxation time, that with two modes closely located, and that represented by the Kohlrausch-Williams-Watts function. We report the first application to experimental data of liquid water. In addition to the two known modes, the existence of a relaxation mode of water molecules with an intermediate time scale has been discovered. We propose that the fast mode might be assigned to an intermolecular motion and the intermediate motion might be assigned to a rotational motion of the water molecules instead of to the fast mode.

Diffusion of Water in Bentonite Clay

Diffusion of water confined in sodium bentonite clay is studied using the quasi-elastic neutron scattering (QENS) technique. Hydration of bentonite clay is characterized by several methods including X-ray diffraction and thermogravimetric measurements. X-ray diffraction shows that the clay is having a well-defined crystalline structure with an interlayer spacing of 13 A. The QENS experiment has been carried out on hydrated as well as dehydrated clay at room temperature. Significant quasi-elastic broadening was observed in case of hydrated bentonite clay whereas dehydrated clay did not show any broadening over the instrument resolution. Analysis of QENS data reveals that diffusion of water occurs through jump diffusion. Both Jump diffusion models having random and Gaussian distribution in jump length are used to describe the observed dynamics. Obtained diffusion coefficient is found to be lower than that of bulk water.

PH Responsiveness of polyelectrolyte dendrimers: a dynamical perspective

A combined quasi-elastic neutron scattering (QENS) and high-resolution solution NMR spectroscopy study was conducted to investigate the internal dynamics of aqueous (D2O) G5 PAMAM dendrimer solutions as a function of molecular protonation at room temperature. Localized motion of the dendrimer segments was clearly exhibited in the QENS data analysis while the global, center-of-mass translational diffusion was measured by NMR. Our results unambiguously demonstrate an increased rapidity in local scale (∼ 3 A) motion upon increasing the molecular protonation. This is contrary to an intuitive picture that increased charge stiffens the dendrimer segments thereby inhibiting local motion. These charge-induced changes may be a result of interactions with the surrounding counterions and water molecules as the segments explore additional intra-dendrimer volume made available by slight electrostatic swelling and redistribution of mass in the dendrimer interior. This observation is relevant to development of a microscopic picture of dendrimer-based packages as guest-molecule delivery vehicles because reorganization of the confining dendrimer segments must be a precursor to guest-molecule release.

Water motion in reverse micelles studied by quasielastic neutron scattering and molecular dynamics simulations.

Motion of water molecules in Aerosol OT [sodium bis(2-ethylhexyl) sulfosuccinate, AOT] reverse micelles with water content w(0) ranging from 1 to 5 has been explored both experimentally through quasielastic neutron scattering (QENS) and with molecular dynamics (MD) simulations. The experiments were performed at the energy resolution of 85 microeV over the momentum transfer (Q) range of 0.36-2.53 A(-1) on samples in which the nonpolar phase (isooctane) and the AOT alkyl chains were deuterated, thereby suppressing their contribution to the QENS signal. QENS results were analyzed via a jump-diffusion/isotropic rotation model, which fits the results reasonably well despite the fact that confinement effects are not explicitly taken into account. This analysis indicates that in reverse micelles with low-water content (w(0)=1 and 2.5) translational diffusion rate is too slow to be detected, while for w(0)=5 the diffusion coefficient is much smaller than for bulk water. Rotational diffusion coefficients obtained from this analysis increase with w(0) and are smaller than for bulk water, but rotational mobility is less drastically reduced than translational mobility. Using the Faeder/Ladanyi model [J. Phys. Chem. B 104, 1033 (2000)] of reverse micelle interior, MD simulations were performed to calculate the self-intermediate scattering function F(S)(Q,t) for water hydrogens. Comparison of the time Fourier transform of this F(S)(Q,t) with the QENS dynamic structure factor S(Q,omega), shows good agreement between the model and experiment. Separate intermediate scattering functions F(S) (R)(Q,t) and F(S) (CM)(Q,t) were determined for rotational and translational motion. Consistent with the decoupling approximation used in the analysis of QENS data, the product of F(S) (R)(Q,t) and F(S) (CM)(Q,t) is a good approximation to the total F(S)(Q,t). We find that the decay of F(S) (CM)(Q,t) is nonexponential and our analysis of the MD data indicates that this behavior is due to lower water mobility close to the interface and to confinement-induced restrictions on the range of translational displacements. Rotational relaxation also exhibits nonexponential decay. However, rotational mobility of O-H bond vectors in the interfacial region remains fairly high due to the lower density of water-water hydrogen bonds in the vicinity of the interface.

Local dynamics of atactic polypropylene across the glass transition

We report a dynamic investigation of the molecular processes in atactic polypropylene using quasi-elastic neutron scattering (QENS). This polymer was investigated over a wide temperature range across the glass transition temperature, T g, using various QENS spectrometers with different energy resolutions. Below T g, methyl side group reorientations take place. We have characterized this motion using a model that accounts for a distribution of activation energies. In the melt, where the polymer chain backbone is no longer frozen in, segmental motion occurs. QENS data analysis allows us to identify three distinct molecular processes and we present evidences for the existence of slow dynamics in the melt.