Rotational dynamics of organic cations in the CH3NH3PbI3 perovskite.

Methylammonium lead iodide (CH3NH3PbI3) based solar cells have shown impressive power conversion efficiencies of above 20%. However, the microscopic mechanism of the high photovoltaic performance is yet to be fully understood. Particularly, the dynamics of CH3NH3(+) cations and their impact on relevant processes such as charge recombination and exciton dissociation are still poorly understood. Here, using elastic and quasi-elastic neutron scattering techniques and group theoretical analysis, we studied rotational modes of the CH3NH3(+) cation in CH3NH3PbI3. Our results show that, in the cubic (T > 327 K) and tetragonal (165 K < T < 327 K) phases, the CH3NH3(+) ions exhibit four-fold rotational symmetry of the C-N axis (C4) along with three-fold rotation around the C-N axis (C3), while in the orthorhombic phase (T < 165 K) only C3 rotation is present. At around room temperature, the characteristic relaxation times for the C4 rotation are found to be τC4 ≈ 5 ps while for the C3 rotation τC3 ≈ 1 ps. The T-dependent rotational relaxation times were fitted with Arrhenius equations to obtain activation energies. Our data show a close correlation between the C4 rotational mode and the temperature dependent dielectric permittivity. Our findings on the rotational dynamics of CH3NH3(+) and the associated dipole have important implications for understanding the low exciton binding energy and a slow charge recombination rate in CH3NH3PbI3 which are directly relevant for the high solar cell performance.

Effects of pressure on the dynamics of an oligomeric protein from deep-sea hyperthermophile.

Inorganic pyrophosphatase (IPPase) from Thermococcus thioreducens is a large oligomeric protein derived from a hyperthermophilic microorganism that is found near hydrothermal vents deep under the sea, where the pressure is up to 100 MPa (1 kbar). It has attracted great interest in biophysical research because of its high activity under extreme conditions in the seabed. In this study, we use the quasielastic neutron scattering (QENS) technique to investigate the effects of pressure on the conformational flexibility and relaxation dynamics of IPPase over a wide temperature range. The ß-relaxation dynamics of proteins was studied in the time ranges from 2 to 25 ps, and from 100 ps to 2 ns, using two spectrometers. Our results indicate that, under a pressure of 100 MPa, close to that of the native environment deep under the sea, IPPase displays much faster relaxation dynamics than a mesophilic model protein, hen egg white lysozyme (HEWL), at all measured temperatures, opposite to what we observed previously under ambient pressure. This contradictory observation provides evidence that the protein energy landscape is distorted by high pressure, which is significantly different for hyperthermophilic (IPPase) and mesophilic (HEWL) proteins. We further derive from our observations a schematic denaturation phase diagram together with energy landscapes for the two very different proteins, which can be used as a general picture to understand the dynamical properties of thermophilic proteins under pressure.

Spin jam induced by quantum fluctuations in a frustrated magnet.

Since the discovery of spin glasses in dilute magnetic systems, their study has been largely focused on understanding randomness and defects as the driving mechanism. The same paradigm has also been applied to explain glassy states found in dense frustrated systems. Recently, however, it has been theoretically suggested that different mechanisms, such as quantum fluctuations and topological features, may induce glassy states in defect-free spin systems, far from the conventional dilute limit. Here we report experimental evidence for existence of a glassy state, which we call a spin jam, in the vicinity of the clean limit of a frustrated magnet, which is insensitive to a low concentration of defects. We have studied the effect of impurities on SrCr9pGa12-9pO19 [SCGO(p)], a highly frustrated magnet, in which the magnetic Cr(3+) (s = 3/2) ions form a quasi-2D triangular system of bipyramids. Our experimental data show that as the nonmagnetic Ga(3+) impurity concentration is changed, there are two distinct phases of glassiness: an exotic glassy state, which we call a spin jam, for the high magnetic concentration region (p > 0.8) and a cluster spin glass for lower magnetic concentration (p < 0.8). This observation indicates that a spin jam is a unique vantage point from which the class of glassy states of dense frustrated magnets can be understood.

Boson peak in deeply cooled confined water: a possible way to explore the existence of the liquid-to-liquid transition in water.

The boson peak in deeply cooled water confined in nanopores is studied with inelastic neutron scattering. We show that in the (P, T) plane, the locus of the emergence of the boson peak is nearly parallel to the Widom line below ∼ 1600 bar. Above 1600 bar, the situation is different and from this difference the end pressure of the Widom line is estimated. The frequency and width of the boson peak correlate with the density of water, which suggests a method to distinguish the hypothetical "low-density liquid" and "high-density liquid" phases in deeply cooled water.

Coherent dynamics of meta-toluidine investigated by quasielastic neutron scattering.

The coherent dynamics of a typical fragile glass former, meta-toluidine, was investigated at the molecular level using quasielastic neutron scattering, with time-of-flight and neutron spin echo spectrometers. It is well known that the static structure factor of meta-toluidine shows a prepeak originating from clustering of the molecules through hydrogen bonding between the amine groups. The dynamics of meta-toluidine was measured for several values of the wavevector transfer Q, which is equivalent to an inverse length scale, in a range encompassing the prepeak and the structure factor peak. Data were collected in the temperature range corresponding to the liquid and supercooled states, down to the glass transition. At least two dynamical processes were identified. This paper focuses on the slowest relaxation process in the system, the α-relaxation, which was found to scale with the macroscopic shear viscosity at all the investigated Q values. No evidence of "de Gennes" narrowing associated with the prepeak was observed, in contrast with what happens at the Q value corresponding to the interparticle distance. Moreover, using partially deuterated samples, the dynamics of the clusters was found to be correlated to the single-particle dynamics of the meta-toluidine molecules.

Vibrational density of states of hydration water at biomolecular sites: hydrophobicity promotes low density amorphous ice behavior.

Inelastic neutron scattering experiments and molecular dynamics simulations have been used to investigate the low frequency modes, in the region between 0 and 100 meV, of hydration water in selected hydrophilic and hydrophobic biomolecules. The results show changes in the plasticity of the hydrogen-bond network of hydration water molecules depending on the biomolecular site. At 200 K, the measured low frequency density of states of hydration water molecules of hydrophilic peptides is remarkably similar to that of high density amorphous ice, whereas, for hydrophobic biomolecules, it is comparable to that of low density amorphous ice behavior. In both hydrophilic and hydrophobic biomolecules, the high frequency modes show a blue shift of the libration mode as compared to the room temperature data. These results can be related to the density of water molecules around the biological interface, suggesting that the apparent local density of water is larger in a hydrophilic environment.

Identifying the specific nanostructures responsible for the high thermoelectric performance of (Bi,Sb)2Te3 nanocomposites.

Herein, we report the synthesis of multiscale nanostructured p-type (Bi,Sb)(2)Te(3) bulk materials by melt-spinning single elements of Bi, Sb, and Te followed by a spark plasma sintering process. The samples that were most optimized with the resulting composition (Bi(0.48)Sb(1.52)Te(3)) and specific nanostructures showed an increase of approximately 50% or more in the figure of merit, ZT, over that of the commercial bulk material between 280 and 475 K, making it suitable for commercial applications related to both power generation and refrigeration. The results of high-resolution electron microscopy and small angle and inelastic neutron scattering along with corresponding thermoelectric property measurements corroborate that the 10-20 nm nanocrystalline domains with coherent boundaries are the key constituent that accounts for the resulting exceptionally low lattice thermal conductivity and significant improvement of ZT.

DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data.

National user facilities such as the NIST Center for Neutron Research (NCNR) require a significant base of software to treat the data produced by their specialized measurement instruments. There is no universally accepted and used data treatment package for the reduction, visualization, and analysis of inelastic neutron scattering data. However, we believe that the software development approach adopted at the NCNR has some key characteristics that have resulted in a successful software package called DAVE (the Data Analysis and Visualization Environment). It is developed using a high level scientific programming language, and it has been widely adopted in the United States and abroad. In this paper we describe the development approach, elements of the DAVE software suite, its usage and impact, and future directions and opportunities for development.

Effects of hydration water on protein methyl group dynamics in solution.

Elastic and quasielastic neutron scattering experiments have been used to investigate the dynamics of methyl groups in a protein-model hydrophobic peptide in solution. The results suggest that, when the hydrophobic side chains are hydrated by a single hydration water layer, the only allowed motions are confined and attributed to librational and rotational movement associated with the methyl groups. They provide unique experimental evidence that the structural and dynamical properties of the interfacial water strongly influence the side-chain dynamics and the activation of diffusive motion.

A comparison of united atom, explicit atom, and coarse-grained simulation models for poly(ethylene oxide).

We compare static and dynamic properties obtained from three levels of modeling for molecular dynamics simulation of poly(ethylene oxide) (PEO). Neutron scattering data are used as a test of each model's accuracy. The three simulation models are an explicit atom (EA) model (all the hydrogens are taken into account explicitly), a united atom (UA) model (CH(2) and CH(3) groups are considered as a single unit), and a coarse-grained (CG) model (six united atoms are taken as one bead). All three models accurately describe the PEO static structure factor as measured by neutron diffraction. Dynamics are assessed by comparison to neutron time of flight data, which follow self-motion of protons. Hydrogen atom motion from the EA model and carbon/oxygen atom motion from the UA model closely follow the experimental hydrogen motion, while hydrogen atoms reinserted in the UA model are too fast. The EA and UA models provide a good description of the orientation properties of C-H vectors measured by nuclear magnetic resonance experiments. Although dynamic observables in the CG model are in excellent agreement with their united atom counterparts, they cannot be compared to neutron data because the time after which the CG model is valid is greater than the neutron decay times.

Molecular view of water dynamics near model peptides.

Incoherent quasi-elastic neutron scattering (QENS) has been used to measure the dynamics of water molecules in solutions of a model protein backbone, N-acetyl-glycine-methylamide (NAGMA), as a function of concentration, for comparison with results for water dynamics in aqueous solutions of the N-acetyl-leucine-methylamide (NALMA) hydrophobic peptide at comparable concentrations. From the analysis of the elastic incoherent structure factor, we find significant fractions of elastic intensity at high and low concentrations for both solutes, which corresponds to a greater population of protons with rotational time scales outside the experimental resolution (>13 ps). The higher-concentration solutions show a component of the elastic fraction that we propose is due to water motions that are strongly coupled to the solute motions, while for low-concentration solutions an additional component is activated due to dynamic coupling between inner and outer hydration layers. An important difference between the solute types at the highest concentration studied is found from stretched exponential fits to their experimental intermediate scattering functions, showing more pronounced anomalous diffusion signatures for NALMA, including a smaller stretched exponent beta and a longer structural relaxation time tau than those found for NAGMA. The more normal water diffusion exhibited near the hydrophilic NAGMA provides experimental support for an explanation of the origin of the anomalous diffusion behavior of NALMA as arising from frustrated interactions between water molecules when a chemical interface is formed upon addition of a hydrophobic side chain, inducing spatial heterogeneity in the hydration dynamics in the two types of regions of the NALMA peptide. We place our QENS measurements on model biological solutes in the context of other spectroscopic techniques and provide both confirming as well as complementary dynamic information that attempts to give a unifying molecular view of hydration dynamics signatures near peptides and proteins.

Neutron Time-of-Flight Spectroscopy.

The time-of-flight technique is employed in two of the instruments at the NIST Cold Neutron Research Facility (CNRF). A pulsed monochromatic beam strikes the sample, and the energies of scattered neutrons are determined from their times-of-flight to an array of detectors. The time-of-flight method may be used in a variety of types of experiments such as studies of vibrational and magnetic excitations, tunneling spectroscopy, and quasielastic scattering studies of diffusional behavior; several examples of experiments are discussed. We also present brief descriptions of the CNRF time-of-flight instruments, including their modi operandi and some of their more pertinent parameters and performance characteristics.