PREFACE: Preface

NASA Astrophysics Data System (ADS)

Hotta, Takashi

2016-02-01

This volume of Journal of Physics: Conference Series contains both invited and contributed papers presented at the International Symposium on "New Quantum Phases Emerging from Novel Crystal Structure", which was held from 24-25 September 2015 at the Minami-Osawa Campus of Tokyo Metropolitan University (TMU). The Graduate School of Science and Engineering of TMU is now promoting a research project on "New Quantum Phases Emerging from Novel Crystal Structure" with the support of the university. This is the cooperative project involving the electrical and electronic engineering and physics departments to discover new quantum phases in strongly correlated electron systems on novel crystal structures, with geometrically characteristic properties such as cage, layered, and geometrical frustrated structures. In this international symposium, we have mainly picked up BiS2-based layered superconductors, cage-structure materials such as 1-2-20 and filled skutterudites, geometrically frustrated systems such as pyrochlore compounds, and noncentrosymmetric materials. Topics on other materials with exotic crystal structure have been also discussed. I believe that this symposium provides a good opportunity to present recent research results on magnetism and superconductivity in such materials, and to discuss future directions of research on strongly correlated electron systems with novel crystal structure. I would like to give thanks, on behalf of the organizing committee, to all participants of the TMU International Symposium and all members of the Advisory Committee, who have contributed to the success of this symposium. I further thank the TMU Research Organization for the financial support of this symposium.

Functional materials discovery using energy-structure-function maps

NASA Astrophysics Data System (ADS)

Pulido, Angeles; Chen, Linjiang; Kaczorowski, Tomasz; Holden, Daniel; Little, Marc A.; Chong, Samantha Y.; Slater, Benjamin J.; McMahon, David P.; Bonillo, Baltasar; Stackhouse, Chloe J.; Stephenson, Andrew; Kane, Christopher M.; Clowes, Rob; Hasell, Tom; Cooper, Andrew I.; Day, Graeme M.

2017-03-01

Molecular crystals cannot be designed in the same manner as macroscopic objects, because they do not assemble according to simple, intuitive rules. Their structures result from the balance of many weak interactions, rather than from the strong and predictable bonding patterns found in metal-organic frameworks and covalent organic frameworks. Hence, design strategies that assume a topology or other structural blueprint will often fail. Here we combine computational crystal structure prediction and property prediction to build energy-structure-function maps that describe the possible structures and properties that are available to a candidate molecule. Using these maps, we identify a highly porous solid, which has the lowest density reported for a molecular crystal so far. Both the structure of the crystal and its physical properties, such as methane storage capacity and guest-molecule selectivity, are predicted using the molecular structure as the only input. More generally, energy-structure-function maps could be used to guide the experimental discovery of materials with any target function that can be calculated from predicted crystal structures, such as electronic structure or mechanical properties.

Functional materials discovery using energy-structure-function maps.

PubMed

Pulido, Angeles; Chen, Linjiang; Kaczorowski, Tomasz; Holden, Daniel; Little, Marc A; Chong, Samantha Y; Slater, Benjamin J; McMahon, David P; Bonillo, Baltasar; Stackhouse, Chloe J; Stephenson, Andrew; Kane, Christopher M; Clowes, Rob; Hasell, Tom; Cooper, Andrew I; Day, Graeme M

2017-03-30

Molecular crystals cannot be designed in the same manner as macroscopic objects, because they do not assemble according to simple, intuitive rules. Their structures result from the balance of many weak interactions, rather than from the strong and predictable bonding patterns found in metal-organic frameworks and covalent organic frameworks. Hence, design strategies that assume a topology or other structural blueprint will often fail. Here we combine computational crystal structure prediction and property prediction to build energy-structure-function maps that describe the possible structures and properties that are available to a candidate molecule. Using these maps, we identify a highly porous solid, which has the lowest density reported for a molecular crystal so far. Both the structure of the crystal and its physical properties, such as methane storage capacity and guest-molecule selectivity, are predicted using the molecular structure as the only input. More generally, energy-structure-function maps could be used to guide the experimental discovery of materials with any target function that can be calculated from predicted crystal structures, such as electronic structure or mechanical properties.

Physical and Structural Studies on the Cryo-cooling of Insulin Crystals

NASA Technical Reports Server (NTRS)

Lovelace, J.; Bellamy, H.; Snell, E. H.; Borgstahl, G.

2003-01-01

Reflection profiles were analyzed from microgravity-(mg) and earth-grown insulin crystals to measure mosaicity (h) and to reveal mosaic domain structure and composition. The effects of cryocooling on single and multi-domain crystals were compared. The effects of cryocooling on insulin structure were also re-examined. Microgravity crystals were larger, more homogeneous, and more perfect than earth crystals. Several mg crystals contained primarily a single mosaic domain with havg of 0.005deg. The earth crystals varied in quality and all contained multiple domains with havg of 0.031deg. Cryocooling caused a 43-fold increase in h for mg crystals (havg=0.217deg) and an %fold increase for earth crystals (havg=0.246deg). These results indicate that very well-ordered crystals are not completely protected from the stresses associated with cryocooling, especially when structural perturbations occur. However, there were differences in the reflection profiles. For multi-mosaic domain crystals, each domain individually broadened and separated from the other domains upon cryo-cooling. Cryo-cooling did not cause an increase in the number of domains. A crystal composed of a single domain retained this domain structure and the reflection profiles simply broadened. Therefore, an improved signal-to-noise ratio for each reflection was measured from cryo-cooled single domain crystals relative to cryo-cooled multi-domain crystals. This improved signal, along with the increase in crystal size, facilitated the measurement of the weaker high- resolution reflections. The observed broadening of reflection profiles indicates increased variation in unit cell dimensions which may be linked to cryo-cooling-associated structural changes and disorder.

Study of rare earth local moment magnetism and strongly correlated phenomena in various crystal structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kong, Tai

Benefiting from unique properties of 4f electrons, rare earth based compounds are known for offering a versatile playground for condensed matter physics research as well as industrial applications. This thesis focuses on three specific examples that further explore the rare earth local moment magnetism and strongly correlated phenomena in various crystal structures.

Structure, Hydrodynamics, and Phase Transition of Freely Suspended Liquid Crystals

NASA Technical Reports Server (NTRS)

Clark, Noel A.

2000-01-01

Smectic liquid crystals are phases of rod shaped molecules organized into one dimensionally (1D) periodic arrays of layers, each layer being between one and two molecular lengths thick. In the least ordered smectic phases, the smectics A and C, each layer is a two dimensional (2D) liquid. Additionally there are a variety of more ordered smectic phases having hexatic short range translational order or 2D crystalline quasi long range translational order within the layers. The inherent fluid-layer structure and low vapor pressure of smectic liquid crystals enable the long term stabilization of freely suspended, single component, layered fluid films as thin as 30A, a single molecular layer. The layering forces the films to be an integral number of smectic layers thick, quantizing their thickness in layer units and forcing a film of a particular number of layers to be physically homogeneous with respect to its layer structure over its entire area. Optical reflectivity enables the precise determination of the number of layers. These ultrathin freely suspended liquid crystal films are structures of fundamental interest in condensed matter and fluid physics. They are the thinnest known stable condensed phase fluid structures and have the largest surface-to-volume ratio of any stable fluid preparation, making them ideal for the study of the effects of reduced dimensionality on phase behavior and on fluctuation and interface phenomena. Their low vapor pressure and quantized thickness enable the effective use of microgravity to extend the study of basic capillary phenomena to ultrathin fluid films. Freely suspended films have been a wellspring of new liquid crystal physics. They have been used to provide unique experimental conditions for the study of condensed phase transitions in two dimensions. They are the only system in which the hexatic has been unambiguously identified as a phase of matter, and the only physical system in which fluctuations of a 2D XY system and Kosterlitz Thouless phase transition has been observed and 2D XY quasi long range order verified. Smectic films have enabled the precise determination of smectic layer electron density and positional fluctuation profile and have been used to show that the interlayer interactions in anti-ferroelectric tilted smectics do not extend significantly beyond nearest neighbors. The interactions which are operative in liquid crystals are generally weak in comparison to those in crystalline phases, leading to the facile manipulation of the order in liquid crystals by external agents such as applied fields and surfaces. Effects arising from weak ordering are significantly enhanced in ultrathin free films and filaments wherein the intermolecular coupling is effectively reduced by loss of neighbors. Over the past four years this research, which we now detail, has produced a host of exciting new discoveries and unexpected results, maintaining the position of the study of freely suspended liquid crystal structures as one of most exciting and fruitful areas of complex fluid physics. In addition, several potentially interesting microgravity free film experiments have been identified.

Thermo-Physical Properties of B2O3-Containing Mold Flux for High Carbon Steels in Thin Slab Continuous Casters: Structure, Viscosity, Crystallization, and Wettability

NASA Astrophysics Data System (ADS)

Park, Jun-Yong; Kim, Gi Hyun; Kim, Jong Bae; Park, Sewoong; Sohn, Il

2016-08-01

The effect of B2O3 on the thermo-physical properties of commercial mold fluxes, including the viscosity, crystallization behavior, and wettability, was investigated. Viscosity was measured using the rotating spindle method, and CCT (continuous cooling transformation) diagrams were obtained to investigate the crystallization behavior at various cooling rates using CLSM (confocal laser scanning microscope). The wettability of the fluxes was determined by measuring the contact angles at 1573 K (1300 °C) using the digital images generated by the sessile drop method and were used to calculate the surface tension, interfacial tension, and work of adhesion for Flux A (existing flux) and B (modified flux). These thermo-physical properties were correlated with the structural analysis obtained using FT-IR (Fourier transform-infrared), Raman and MAS-NMR (magic angle spin-nuclear magnetic resonance) spectroscopy. In addition, DTA (differential thermal analysis) was performed on the samples to measure the liquidus temperatures. Higher B2O3 concentrations resulted in lower liquidus temperatures, consequently decreasing the viscosity, the break temperature, and the crystallization temperature. However, B2O3 addition accelerated crystal growth owing to the higher diffusion kinetics of the cations, which also reduced the size of the liquid/solid co-existing region.

A crystal plasticity model for slip in hexagonal close packed metals based on discrete dislocation simulations

NASA Astrophysics Data System (ADS)

Messner, Mark C.; Rhee, Moono; Arsenlis, Athanasios; Barton, Nathan R.

2017-06-01

This work develops a method for calibrating a crystal plasticity model to the results of discrete dislocation (DD) simulations. The crystal model explicitly represents junction formation and annihilation mechanisms and applies these mechanisms to describe hardening in hexagonal close packed metals. The model treats these dislocation mechanisms separately from elastic interactions among populations of dislocations, which the model represents through a conventional strength-interaction matrix. This split between elastic interactions and junction formation mechanisms more accurately reproduces the DD data and results in a multi-scale model that better represents the lower scale physics. The fitting procedure employs concepts of machine learning—feature selection by regularized regression and cross-validation—to develop a robust, physically accurate crystal model. The work also presents a method for ensuring the final, calibrated crystal model respects the physical symmetries of the crystal system. Calibrating the crystal model requires fitting two linear operators: one describing elastic dislocation interactions and another describing junction formation and annihilation dislocation reactions. The structure of these operators in the final, calibrated model reflect the crystal symmetry and slip system geometry of the DD simulations.

Interactions of biomacromolecules with reverse hexagonal liquid crystals: drug delivery and crystallization applications.

PubMed

Libster, Dima; Aserin, Abraham; Garti, Nissim

2011-04-15

Recently, self-assembled lyotropic liquid crystals (LLCs) of lipids and water have attracted the attention of both scientific and applied research communities, due to their remarkable structural complexity and practical potential in diverse applications. The phase behavior of mixtures of glycerol monooleate (monoolein, GMO) was particularly well studied due to the potential utilization of these systems in drug delivery systems, food products, and encapsulation and crystallization of proteins. Among the studied lyotropic mesophases, reverse hexagonal LLC (H(II)) of monoolein/water were not widely subjected to practical applications since these were stable only at elevated temperatures. Lately, we obtained stable H(II) mesophases at room temperature by incorporating triacylglycerol (TAG) molecules into the GMO/water mixtures and explored the physical properties of these structures. The present feature article summarizes recent systematic efforts in our laboratory to utilize the H(II) mesophases for solubilization, and potential release and crystallization of biomacromolecules. Such a concept was demonstrated in the case of two therapeutic peptides-cyclosporin A (CSA) and desmopressin, as well as RALA peptide, which is a model skin penetration enhancer, and eventually a larger macromolecule-lysozyme (LSZ). In the course of the study we tried to elucidate relationships between the different levels of organization of LLCs (from the microstructural level, through mesoscale, to macroscopic level) and find feasible correlations between them. Since the structural properties of the mesophase systems are a key factor in drug release applications, we investigated the effects of these guest molecules on their conformations and the way these molecules partition within the domains of the mesophases. The examined H(II) mesophases exhibited great potential as transdermal delivery vehicles for bioactive peptides, enabling tuning the release properties according to their chemical composition and physical properties. Furthermore, we showed a promising opportunity for crystallization of CSA and LSZ in single crystal form as model biomacromolecules for crystallographic structure determination. The main outcomes of our research demonstrated that control of the physical properties of hexagonal LLC on different length scales is key for rational design of these systems as delivery vehicles and crystallization medium for biomacromolecules. Copyright © 2011 Elsevier Inc. All rights reserved.

A hybrid computational-experimental approach for automated crystal structure solution

NASA Astrophysics Data System (ADS)

Meredig, Bryce; Wolverton, C.

2013-02-01

Crystal structure solution from diffraction experiments is one of the most fundamental tasks in materials science, chemistry, physics and geology. Unfortunately, numerous factors render this process labour intensive and error prone. Experimental conditions, such as high pressure or structural metastability, often complicate characterization. Furthermore, many materials of great modern interest, such as batteries and hydrogen storage media, contain light elements such as Li and H that only weakly scatter X-rays. Finally, structural refinements generally require significant human input and intuition, as they rely on good initial guesses for the target structure. To address these many challenges, we demonstrate a new hybrid approach, first-principles-assisted structure solution (FPASS), which combines experimental diffraction data, statistical symmetry information and first-principles-based algorithmic optimization to automatically solve crystal structures. We demonstrate the broad utility of FPASS to clarify four important crystal structure debates: the hydrogen storage candidates MgNH and NH3BH3; Li2O2, relevant to Li-air batteries; and high-pressure silane, SiH4.

Synthesis and structural characterization of bulk Sb2Te3 single crystal

NASA Astrophysics Data System (ADS)

Sultana, Rabia; Gahtori, Bhasker; Meena, R. S.; Awana, V. P. S.

2018-05-01

We report the growth and characterization of bulk Sb2Te3 single crystal synthesized by the self flux method via solid state reaction route from high temperature melt (850˚C) and slow cooling (2˚C/hour) of constituent elements. The single crystal X-ray diffraction pattern showed the 00l alignment and the high crystalline nature of the resultant sample. The rietveld fitted room temperature powder XRD revealed the phase purity and rhombohedral structure of the synthesized crystal. The formation and analysis of unit cell structure further verified the rhombohedral structure composed of three quintuple layers stacked one over the other. The SEM image showed the layered directional growth of the synthesized crystal carried out using the ZEISS-EVOMA-10 scanning electron microscope The electrical resistivity measurement was carried out using the conventional four-probe method on a quantum design Physical Property Measurement System (PPMS). The temperature dependent electrical resistivity plot for studied Sb2Te3 single crystal depicts metallic behaviour in the absence of any applied magnetic field. The synthesis as well as the structural characterization of as grown Sb2Te3 single crystal is reported and discussed in the present letter.

Artificial crystals with 3d metal and palladium particles subjected to high-temperature heat treatment

NASA Astrophysics Data System (ADS)

Rinkevich, A. B.; Nemytova, O. V.; Perov, D. V.; Samoylovich, M. I.; Kuznetsov, E. A.

2018-04-01

High-temperature heat treatment has valuable impact on the structure and physical properties of artificial crystals with 3d metal and palladium particles. Artificial crystals are obtained by means of introduction of particles into the interspherical voids of opal matrices. The magnetic properties are studied at the temperatures ranging from 2 to 300 K and in fields up to 350 kOe. Microwave properties are investigated in the millimeter frequency range. The complex dielectric permittivity of several nanocomposites is measured. The influence of heat treatment up to 960 °C on the structure of artificial crystals is clarified.

Distinct molecular structures and hydrogen bond patterns of α,α-diethyl-substituted cyclic imide, lactam, and acetamide derivatives in the crystalline phase

NASA Astrophysics Data System (ADS)

Krivoshein, Arcadius V.; Ordonez, Carlos; Khrustalev, Victor N.; Timofeeva, Tatiana V.

2016-10-01

α,α-Dialkyl- and α-alkyl-α-aryl-substituted cyclic imides, lactams, and acetamides show promising anticonvulsant, anxiolytic, and anesthetic activities. While a number of crystal structures of various α-substituted cyclic imides, lactams, and acetamides were reported, no in-depth comparison of crystal structures and solid-state properties of structurally matched compounds have been carried out so far. In this paper, we report molecular structure and intermolecular interactions of three α,α-diethyl-substituted compounds - 3,3-diethylpyrrolidine-2,5-dione, 3,3-diethylpyrrolidin-2-one, and 2,2-diethylacetamide - in the crystalline phase, as studied using single-crystal X-ray diffraction and IR spectroscopy. We found considerable differences in the patterns of H-bonding and packing of the molecules in crystals. These differences correlate with the compounds' melting points and are of significance to physical pharmacy and formulation development of neuroactive drugs.

A Fundamental Study of Inorganic Clathrate and Other Open-Framework Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nolas, George

Due to formidable synthetic challenges, many materials of scientific and technological interest are first obtained as microcrystalline powders. High purity, high yield processing techniques are often lacking and thus care must be taken in interpretation of the observed structural, chemical, and physical properties of powder or polycrystalline materials, which can be strongly influenced by extrinsic properties. Furthermore, the preparation of high-quality single crystals for many materials by traditional techniques can be especially challenging in cases where the elemental constituents have greatly differing melting points and/or vapor pressures, when the desired compound is thermodynamically metastable, or where growth with participation ofmore » the melt is generally not possible. New processing techniques are therefore imperative in order to investigate the intrinsic properties of these materials and elucidate their fundamental physical properties. Intermetallic clathrates constitute one such class of materials. The complex crystal structures of intermetallic clathrates are characterized by mainly group 14 host frameworks encapsulating guest-ions in polyhedral cages. The unique features of clathrate structures are intimately related to their physical properties, offering ideal systems for the study of structure-property relationships in crystalline solids. Moreover, intermetallic clathrates are being actively investigated due to their potential for application in thermoelectrics, photovoltaics and opto-electronics, superconductivity, and magnetocaloric technologies. We have developed different processing techniques in order to synthesize phase-pure high yield clathrates reproducibly, as well as grow single crystals for the first time. We also employed these techniques to synthesize new “open-framework” compounds. These advances in materials processing and crystal growth allowed for the investigation of the physical properties of a variety of different clathrate compositions for the first time.« less

DiffPy-CMI-Python libraries for Complex Modeling Initiative

DOE Office of Scientific and Technical Information (OSTI.GOV)

Billinge, Simon; Juhas, Pavol; Farrow, Christopher

2014-02-01

Software to manipulate and describe crystal and molecular structures and set up structural refinements from multiple experimental inputs. Calculation and simulation of structure derived physical quantities. Library for creating customized refinements of atomic structures from available experimental and theoretical inputs.

Organic semiconductor crystals.

PubMed

Wang, Chengliang; Dong, Huanli; Jiang, Lang; Hu, Wenping

2018-01-22

Organic semiconductors have attracted a lot of attention since the discovery of highly doped conductive polymers, due to the potential application in field-effect transistors (OFETs), light-emitting diodes (OLEDs) and photovoltaic cells (OPVs). Single crystals of organic semiconductors are particularly intriguing because they are free of grain boundaries and have long-range periodic order as well as minimal traps and defects. Hence, organic semiconductor crystals provide a powerful tool for revealing the intrinsic properties, examining the structure-property relationships, demonstrating the important factors for high performance devices and uncovering fundamental physics in organic semiconductors. This review provides a comprehensive overview of the molecular packing, morphology and charge transport features of organic semiconductor crystals, the control of crystallization for achieving high quality crystals and the device physics in the three main applications. We hope that this comprehensive summary can give a clear picture of the state-of-art status and guide future work in this area.

Band structure of an electron in a kind of periodic potentials with singularities

NASA Astrophysics Data System (ADS)

Hai, Kuo; Yu, Ning; Jia, Jiangping

2018-06-01

Noninteracting electrons in some crystals may experience periodic potentials with singularities and the governing Schrödinger equation cannot be defined at the singular points. The band structure of a single electron in such a one-dimensional crystal has been calculated by using an equivalent integral form of the Schrödinger equation. Both the perturbed and exact solutions are constructed respectively for the cases of a general singular weak-periodic system and its an exactly solvable version, Kronig-Penney model. Any one of them leads to a special band structure of the energy-dependent parameter, which results in an effective correction to the previous energy-band structure and gives a new explanation for forming the band structure. The used method and obtained results could be a valuable aid in the study of energy bands in solid-state physics, and the new explanation may trigger investigation to different physical mechanism of electron band structures.

Space-Time Crystal and Space-Time Group

NASA Astrophysics Data System (ADS)

Xu, Shenglong; Wu, Congjun

2018-03-01

Crystal structures and the Bloch theorem play a fundamental role in condensed matter physics. We extend the static crystal to the dynamic "space-time" crystal characterized by the general intertwined space-time periodicities in D +1 dimensions, which include both the static crystal and the Floquet crystal as special cases. A new group structure dubbed a "space-time" group is constructed to describe the discrete symmetries of a space-time crystal. Compared to space and magnetic groups, the space-time group is augmented by "time-screw" rotations and "time-glide" reflections involving fractional translations along the time direction. A complete classification of the 13 space-time groups in one-plus-one dimensions (1 +1 D ) is performed. The Kramers-type degeneracy can arise from the glide time-reversal symmetry without the half-integer spinor structure, which constrains the winding number patterns of spectral dispersions. In 2 +1 D , nonsymmorphic space-time symmetries enforce spectral degeneracies, leading to protected Floquet semimetal states. We provide a general framework for further studying topological properties of the (D +1 )-dimensional space-time crystal.

Space-Time Crystal and Space-Time Group.

PubMed

Xu, Shenglong; Wu, Congjun

2018-03-02

Crystal structures and the Bloch theorem play a fundamental role in condensed matter physics. We extend the static crystal to the dynamic "space-time" crystal characterized by the general intertwined space-time periodicities in D+1 dimensions, which include both the static crystal and the Floquet crystal as special cases. A new group structure dubbed a "space-time" group is constructed to describe the discrete symmetries of a space-time crystal. Compared to space and magnetic groups, the space-time group is augmented by "time-screw" rotations and "time-glide" reflections involving fractional translations along the time direction. A complete classification of the 13 space-time groups in one-plus-one dimensions (1+1D) is performed. The Kramers-type degeneracy can arise from the glide time-reversal symmetry without the half-integer spinor structure, which constrains the winding number patterns of spectral dispersions. In 2+1D, nonsymmorphic space-time symmetries enforce spectral degeneracies, leading to protected Floquet semimetal states. We provide a general framework for further studying topological properties of the (D+1)-dimensional space-time crystal.

Structural phase transition in monolayer MoTe2 driven by electrostatic doping

NASA Astrophysics Data System (ADS)

Wang, Ying; Xiao, Jun; Zhu, Hanyu; Li, Yao; Alsaid, Yousif; Fong, King Yan; Zhou, Yao; Wang, Siqi; Shi, Wu; Wang, Yuan; Zettl, Alex; Reed, Evan J.; Zhang, Xiang

2017-10-01

Monolayers of transition-metal dichalcogenides (TMDs) exhibit numerous crystal phases with distinct structures, symmetries and physical properties. Exploring the physics of transitions between these different structural phases in two dimensions may provide a means of switching material properties, with implications for potential applications. Structural phase transitions in TMDs have so far been induced by thermal or chemical means; purely electrostatic control over crystal phases through electrostatic doping was recently proposed as a theoretical possibility, but has not yet been realized. Here we report the experimental demonstration of an electrostatic-doping-driven phase transition between the hexagonal and monoclinic phases of monolayer molybdenum ditelluride (MoTe2). We find that the phase transition shows a hysteretic loop in Raman spectra, and can be reversed by increasing or decreasing the gate voltage. We also combine second-harmonic generation spectroscopy with polarization-resolved Raman spectroscopy to show that the induced monoclinic phase preserves the crystal orientation of the original hexagonal phase. Moreover, this structural phase transition occurs simultaneously across the whole sample. This electrostatic-doping control of structural phase transition opens up new possibilities for developing phase-change devices based on atomically thin membranes.

Physics of smectic membranes

NASA Astrophysics Data System (ADS)

Pieranski, P.; Beliard, L.; Tournellec, J.-Ph.; Leoncini, X.; Furtlehner, C.; Dumoulin, H.; Riou, E.; Jouvin, B.; Fénerol, J.-P.; Palaric, Ph.; Heuving, J.; Cartier, B.; Kraus, I.

1993-03-01

Due to their layered structure, smectic liquid crystals can form membranes, similar to soap bubbles, that can be spanned on frames. Such smectic membranes have been used extensively as samples in many structural X-ray studies of smectic liquid crystals. In this context they have been considered as very convenient and highly perfect samples but little attention has been paid to the reasons for their existence and to the process of their formation. Our aim here is to address a first list of questions, which are the most urgent to answer. We will also describe experiments and models that have been conceived especially in order to understand the physics of these fascinating systems.

Electrical, Thermal, and Magnetic Properties of Single Crystal CaMn2O4 Marokite

NASA Astrophysics Data System (ADS)

White, B. D.; Neumeier, J. J.; Souza, J. A.; Chiorescu, C.; Cohn, J. L.

2008-03-01

CaMn2O4 was first described [1] in 1963 as a natural mineral called Marokite. Since its discovery, it has been studied as a minor structural impurity phase in CMR- related CaMnO3 and for its structural similarities to high-pressure phases of spinel-oxide compounds. However, little attention has previously been paid to physical properties beyond its temperature-dependent magnetization. We will present a detailed physical properties study of CaMn2O4 single crystals grown by the optical floating zone method. [2] These measurements, several of which display anisotropy as a result of an orthorhombic crystal structure, include electrical transport, thermal transport, thermal expansion, heat capacity, and magnetization. [1] C. Gaudefroy, G. Jouravsky, F. Permingeat, Bull. Soc. Franc. Min'er. Crist. 86 (1963) 359. [2] B. D. White, C. A. M. dos Santos, J. A. Souza, K. J. McClellan, J. J. Neumeier submitted to J. Cryst. Growth.

Density functional theory in the solid state

PubMed Central

Hasnip, Philip J.; Refson, Keith; Probert, Matt I. J.; Yates, Jonathan R.; Clark, Stewart J.; Pickard, Chris J.

2014-01-01

Density functional theory (DFT) has been used in many fields of the physical sciences, but none so successfully as in the solid state. From its origins in condensed matter physics, it has expanded into materials science, high-pressure physics and mineralogy, solid-state chemistry and more, powering entire computational subdisciplines. Modern DFT simulation codes can calculate a vast range of structural, chemical, optical, spectroscopic, elastic, vibrational and thermodynamic phenomena. The ability to predict structure–property relationships has revolutionized experimental fields, such as vibrational and solid-state NMR spectroscopy, where it is the primary method to analyse and interpret experimental spectra. In semiconductor physics, great progress has been made in the electronic structure of bulk and defect states despite the severe challenges presented by the description of excited states. Studies are no longer restricted to known crystallographic structures. DFT is increasingly used as an exploratory tool for materials discovery and computational experiments, culminating in ex nihilo crystal structure prediction, which addresses the long-standing difficult problem of how to predict crystal structure polymorphs from nothing but a specified chemical composition. We present an overview of the capabilities of solid-state DFT simulations in all of these topics, illustrated with recent examples using the CASTEP computer program. PMID:24516184

Soft matter perspective on protein crystal assembly.

PubMed

Fusco, Diana; Charbonneau, Patrick

2016-01-01

Crystallography may be the gold standard of protein structure determination, but obtaining the necessary high-quality crystals is also in some ways akin to prospecting for the precious metal. The tools and models developed in soft matter physics to understand colloidal assembly offer some insights into the problem of crystallizing proteins. This topical review describes the various analogies that have been made between proteins and colloids in that context. We highlight the explanatory power of patchy particle models, but also the challenges of providing guidance for crystallizing specific proteins. We conclude with a presentation of possible future research directions. This review is intended for soft matter scientists interested in protein crystallization as a self-assembly problem, and as an introduction to the pertinent physics literature for protein scientists more generally. Copyright © 2015 Elsevier B.V. All rights reserved.

Anisotropy of electrical resistivity in PVT grown WSe2-x crystals

NASA Astrophysics Data System (ADS)

Solanki, G. K.; Patel, Y. A.; Agarwal, M. K.

2018-05-01

Single crystals of p-type WSe2 and WSe1.9 were grown by a physical vapour transport technique. The anisotropy in d.c. electrical resistivity was investigated in these grown crystals. The off-stoichiometric WSe1.9 exhibited a higher anisotropy ratio as compared to WSe2 crystals. The electron microscopic examination revealed the presence of a large number of stacking faults in these crystals. The resistivity enhancement along the c-axis and anisotropic effective mass ratio explained on the basis of structural disorder introduced due to off-stoichiometry.

Unusual structural phase transition in [N(C2H5)4][N(CH3)4][ZnBr4

NASA Astrophysics Data System (ADS)

Krawczyk, Monika K.; Ingram, Adam; Cach, Ryszard; Czapla, Zbigniew; Czupiński, Olaf; Dacko, Sławomir; Staniorowski, Piotr

2018-04-01

The new hybrid organic-inorganic crystal [N(C2H5)4][N(CH3)4][ZnBr4] was grown and its physical properties and structural phase transition are presented. On the basis of thermal analysis (DSC (differential scanning calorimetry), DTA (differential thermal analysis), DTG), X-ray structural, dilatometric and dielectric studies as well as optical observation, the reversible first-order phase transition at 490/488 K on heating and cooling run, respectively, has been found. An appearance of domain structure of ferroelastic type gives evidence for an untypical lowering of crystal symmetry during the phase transition. At room temperature, the satisfying crystal structure solution was found in the tetragonal system, in the P?21m space group.

Crystallization modifiers in lipid systems.

PubMed

Ribeiro, Ana Paula Badan; Masuchi, Monise Helen; Miyasaki, Eriksen Koji; Domingues, Maria Aliciane Fontenele; Stroppa, Valter Luís Zuliani; de Oliveira, Glazieli Marangoni; Kieckbusch, Theo Guenter

2015-07-01

Crystallization of fats is a determinant physical event affecting the structure and properties of fat-based products. The stability of these processed foods is regulated by changes in the physical state of fats and alterations in their crystallization behavior. Problems like polymorphic transitions, oil migration, fat bloom development, slow crystallization and formation of crystalline aggregates stand out. The change of the crystallization behavior of lipid systems has been a strategic issue for the processing of foods, aiming at taylor made products, reducing costs, improving quality, and increasing the applicability and stability of different industrial fats. In this connection, advances in understanding the complex mechanisms that govern fat crystallization led to the development of strategies in order to modulate the conventional processes of fat structuration, based on the use of crystallization modifiers. Different components have been evaluated, such as specific triacyglycerols, partial glycerides (monoacylglycerols and diacylglycerols), free fatty acids, phospholipids and emulsifiers. The knowledge and expertise on the influence of these specific additives or minor lipids on the crystallization behavior of fat systems represents a focus of current interest for the industrial processing of oils and fats. This article presents a comprehensive review on the use of crystallization modifiers in lipid systems, especially for palm oil, cocoa butter and general purpose fats, highlighting: i) the removal, addition or fractionation of minor lipids in fat bases; ii) the use of nucleating agents to modify the crystallization process; iii) control of crystallization in lipid bases by using emulsifiers. The addition of these components into lipid systems is discussed in relation to the phenomena of nucleation, crystal growth, morphology, thermal behavior and polymorphism, with the intention of providing the reader with a complete panorama of the associated mechanisms with crystallization of fats and oils.

Crystal structure, electronic structure, optical and scintillation properties of self-activated Cs 4YbI 6 [Crystal structure, optical and scintillation properties of self-activated Cs 4YbI 6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yuntao; Chakoumakos, Bryan C.; Shi, Hongliang

A self-activated Cs 4YbI 6 single crystal was grown by the vertical Bridgman method. Crystal structure refinements verified the phase purity and the trigonal crystal system with a space group of more » $$\\bar{R}$$3 c. By using differential scanning calorimetry, the melting and crystallization points were determined to be 550 and 510 °C, respectively. Luminescence and scintillation properties were systematically studied. Upon ultraviolet light (360 nm) excitation, the Cs 4YbI 6 crystal exhibits bluish-green emission centered at 450 and 480 nm due to spin-allowed and spin-forbidden transitions of Yb 2+ activators. The lifetimes of the corresponding emission bands at room temperature are tens and hundreds of nanoseconds, respectively. X-ray excited radioluminescence spectrum is dominated by the spin-forbidden transition of Yb 2+ at 480 nm. The absolute light yield is 2700 ± 200 photons/MeV with a principal scintillation decay time of 33 ns. In conclusion, the physical explanation for the low light yield observed is proposed from experimental and theoretical insights.« less

Crystal structure, electronic structure, optical and scintillation properties of self-activated Cs 4YbI 6 [Crystal structure, optical and scintillation properties of self-activated Cs 4YbI 6

DOE PAGES

Wu, Yuntao; Chakoumakos, Bryan C.; Shi, Hongliang; ...

2018-05-14

A self-activated Cs 4YbI 6 single crystal was grown by the vertical Bridgman method. Crystal structure refinements verified the phase purity and the trigonal crystal system with a space group of more » $$\\bar{R}$$3 c. By using differential scanning calorimetry, the melting and crystallization points were determined to be 550 and 510 °C, respectively. Luminescence and scintillation properties were systematically studied. Upon ultraviolet light (360 nm) excitation, the Cs 4YbI 6 crystal exhibits bluish-green emission centered at 450 and 480 nm due to spin-allowed and spin-forbidden transitions of Yb 2+ activators. The lifetimes of the corresponding emission bands at room temperature are tens and hundreds of nanoseconds, respectively. X-ray excited radioluminescence spectrum is dominated by the spin-forbidden transition of Yb 2+ at 480 nm. The absolute light yield is 2700 ± 200 photons/MeV with a principal scintillation decay time of 33 ns. In conclusion, the physical explanation for the low light yield observed is proposed from experimental and theoretical insights.« less

Fundamental Studies of Crystal Growth of Microporous Materials

NASA Technical Reports Server (NTRS)

Singh, Ramsharan; Doolittle, John, Jr.; Payra, Pramatha; Dutta, Prabir K.; George, Michael A.; Ramachandran, Narayanan; Schoeman, Brian J.

2003-01-01

Microporous materials are framework structures with well-defined porosity, often of molecular dimensions. Zeolites contain aluminum and silicon atoms in their framework and are the most extensively studied amongst all microporous materials. Framework structures with P, Ga, Fe, Co, Zn, B, Ti and a host of other elements have also been made. Typical synthesis of microporous materials involve mixing the framework elements (or compounds, thereof) in a basic solution, followed by aging in some cases and then heating at elevated temperatures. This process is termed hydrothermal synthesis, and involves complex chemical and physical changes. Because of a limited understanding of this process, most synthesis advancements happen by a trial and error approach. There is considerable interest in understanding the synthesis process at a molecular level with the expectation that eventually new framework structures will be built by design. The basic issues in the microporous materials crystallization process include: (a) Nature of the molecular units responsible for the crystal nuclei formation; (b) Nature of the nuclei and nucleation process; (c) Growth process of the nuclei into crystal; (d) Morphological control and size of the resulting crystal; (e) Surface structure of the resulting crystals; and (f) Transformation of frameworks into other frameworks or condensed structures.

Sfg

NASA Astrophysics Data System (ADS)

Fischer, R. X.; Baur, W. H.

This document is part of Subvolume E `Zeolite-Type Crystal Structures and their Chemistry. Framework Type Codes RON to STI' of Volume 14 `Microporous and other Framework Materials with Zeolite-Type Structures' of Landolt-Börnstein Group IV `Physical Chemistry'.

Vet

NASA Astrophysics Data System (ADS)

Fischer, R. X.; Baur, W. H.

This document is part of Subvolume F 'Zeolite-Type Crystal Structures and their Chemistry. Framework Type Codes STO to ZON' of Volume 14 'Microporous and other Framework Materials with Zeolite-Type Structures' of Landolt-Börnstein Group IV 'Physical Chemistry'.

Teaching Avalanche Safety Courses: Instructional Techniques and Field Exercises.

ERIC Educational Resources Information Center

Watters, Ron

This paper discusses course structure, teaching techniques, and field exercises for enhancing winter travelers' avalanche knowledge and skills. In two class sessions, the course typically consists of a historical perspective; a section on snow physics (clouds, types of snow crystals, effects of riming, identification of precipitated snow crystals,…

Transport properties of RCo_2B_2C with R = Dy, Ho, and Pr single

NASA Astrophysics Data System (ADS)

Duran, Alejandro; Escudero, Roberto

2002-03-01

Single crystals of (Dy, Ho, Pr)Co_2B_2C have been grown by a cold copper crucible method. Metallurgical and structural studies indicate that this borocarbide family melts incongruently and crystallizes as a derivative structure of the ThCr_2Si_2. The family accepts rare earth atoms depending on the type of transition metals used to form the compound. For instance with Ni atoms, all lanthanides ranging from the large lanthanum to lutetium ions are reported to form RNi_2B_2C single crystals, so far no single crystals have been obtained when changing Ni by Cobalt. A comparison of the structural parameters of the RCo_2B_2C with the RNiHo, Pr) compounds indicate that the atomic distance between transition metal atoms contracts with the insertion of the Co ion, resulting in an increasing of the c parameter and decreasing volume. Several recent reports published in the current literature related on the physical properties of RCo_2B_2C (R = rare earth metals and Y) have been only performed on polycrystalline samples, they commonly contain small amounts of second phases. High quality single crystals are necessaries in order to better understand the physical properties, such as anisotropy in the transport and in the magnetic properties. In this report we show magnetic susceptibility and resistivity measurements performed in single crystals in the ab-plane and c direction for 2 - 320 K temperature range for the three single crystals of (Dy, Ho, Pr)Co_2B_2C.

Time crystals: a review

NASA Astrophysics Data System (ADS)

Sacha, Krzysztof; Zakrzewski, Jakub

2018-01-01

Time crystals are time-periodic self-organized structures postulated by Frank Wilczek in 2012. While the original concept was strongly criticized, it stimulated at the same time an intensive research leading to propositions and experimental verifications of discrete (or Floquet) time crystals—the structures that appear in the time domain due to spontaneous breaking of discrete time translation symmetry. The struggle to observe discrete time crystals is reviewed here together with propositions that generalize this concept introducing condensed matter like physics in the time domain. We shall also revisit the original Wilczek’s idea and review strategies aimed at spontaneous breaking of continuous time translation symmetry.

A historical perspective on protein crystallization from 1840 to the present day.

PubMed

Giegé, Richard

2013-12-01

Protein crystallization has been known since 1840 and can prove to be straightforward but, in most cases, it constitutes a real bottleneck. This stimulated the birth of the biocrystallogenesis field with both 'practical' and 'basic' science aims. In the early years of biochemistry, crystallization was a tool for the preparation of biological substances. Today, biocrystallogenesis aims to provide efficient methods for crystal fabrication and a means to optimize crystal quality for X-ray crystallography. The historical development of crystallization methods for structural biology occurred first in conjunction with that of biochemical and genetic methods for macromolecule production, then with the development of structure determination methodologies and, recently, with routine access to synchrotron X-ray sources. Previously, the identification of conditions that sustain crystal growth occurred mostly empirically but, in recent decades, this has moved progressively towards more rationality as a result of a deeper understanding of the physical chemistry of protein crystal growth and the use of idea-driven screening and high-throughput procedures. Protein and nucleic acid engineering procedures to facilitate crystallization, as well as crystallization methods in gelled-media or by counter-diffusion, represent recent important achievements, although the underlying concepts are old. The new nanotechnologies have brought a significant improvement in the practice of protein crystallization. Today, the increasing number of crystal structures deposited in the Protein Data Bank could mean that crystallization is no longer a bottleneck. This is not the case, however, because structural biology projects always become more challenging and thereby require adapted methods to enable the growth of the appropriate crystals, notably macromolecular assemblages. © 2013 FEBS.

Physical aspects of dexibuprofen and racemic ibuprofen.

PubMed

Leising, G; Resel, R; Stelzer, F; Tasch, S; Lanziner, A; Hantich, G

1996-12-01

This article presents a comparative study of ibuprofen materials in their solid state. Ibuprofen crystallizes into two different structures for the S(+) enantiomer (dexibuprofen) and racemic ibuprofen. The crystal structure of ibuprofen, its optical absorption and photoluminescence, and the thermodynamic results (melting point and heat of fusion) are discussed. From these physicochemical properties, the authors conclude that dexibuprofen, which is the most active species pharmaceutically, and racemic ibuprofen are inherently different solid-state materials.

Boron Arsenide and Boron Phosphide for High Temperature and Luminescent Devices. [semiconductor devices - crystal growth/crystal structure

NASA Technical Reports Server (NTRS)

Chu, T. L.

1975-01-01

The crystal growth of boron arsenide and boron phosphide in the form of bulk crystals and epitaxial layers on suitable substrates is discussed. The physical, chemical, and electrical properties of the crystals and epitaxial layers are examined. Bulk crystals of boron arsenide were prepared by the chemical transport technique, and their carrier concentration and Hall mobility were measured. The growth of boron arsenide crystals from high temperature solutions was attempted without success. Bulk crystals of boron phosphide were also prepared by chemical transport and solution growth techniques. Techniques required for the fabrication of boron phosphide devices such as junction shaping, diffusion, and contact formation were investigated. Alloying techniques were developed for the formation of low-resistance ohmic contacts to boron phosphide. Four types of boron phosphide devices were fabricated: (1) metal-insulator-boron phosphide structures, (2) Schottky barriers; (3) boron phosphide-silicon carbide heterojunctions; and (4) p-n homojunctions. Easily visible red electroluminescence was observed from both epitaxial and solution grown p-n junctions.

Intrinsic Topological Insulator Bi1.5Sb0.5Te3-xSex Thin Crystals

NASA Astrophysics Data System (ADS)

Wang, Wei; Li, Li; Zou, Wenqin; He, Liang; Song, Fengqi; Zhang, Rong; Wu, Xiaoshan; Zhang, Fengming

2015-01-01

The quaternary topological insulator (Bi,Sb)2(Te,Se)3 has demonstrated topological surface states with an insulating bulk. Scientists have identified an optimized composition of Bi1.5Sb0.5Te1.7Se1.3 with the highest resistivity reported. But the physics that drive to this composition remains unclear. Here we report the crystal structure and the magneto-transport properties of Bi1.5Sb0.5Te3-xSex (BSTS) series. A correlation between the structure and the physical properties has been revealed. We found out that within the rhombohedral structure, the composition with most Te substituting Se has the highest resistivity. On the other hand, segregation of other composition phases will introduce much higher bulk concentration.

Abinitio powder x-ray diffraction and PIXEL energy calculations on thiophene derived 1,4 dihydropyridine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karthikeyan, N., E-mail: karthin10@gmail.com; Sivakumar, K.; Pachamuthu, M. P.

We focus on the application of powder diffraction data to get abinitio crystal structure determination of thiophene derived 1,4 DHP prepared by cyclocondensation method using solid catalyst. Crystal structure of the compound has been solved by direct-space approach on Monte Carlo search in parallel tempering mode using FOX program. Initial atomic coordinates were derived using Gaussian 09W quantum chemistry software in semi-empirical approach and Rietveld refinement was carried out using GSAS program. The crystal structure of the compound is stabilized by one N-H…O and three C-H…O hydrogen bonds. PIXEL lattice energy calculation was carried out to understand the physical naturemore » of intermolecular interactions in the crystal packing, on which the total lattice energy is contributed into Columbic, polarization, dispersion, and repulsion energies.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Yiming; Fredrickson, Daniel C.

Intermetallic crystal structures offer an enormous structural diversity, with an endless array of structural motifs whose connection to stability and physical properties are often mysterious. Making sense of the often complex crystal structures that arise here, developing a clear structural description, and identifying connections to other phases can be laborious and require an encyclopedic knowledge of structure types. In this Article, we present PRINCEPS, an algorithm based on a new coordination environment projection scheme that facilitates the structural analysis and comparison of such crystal structures. We demonstrate the potential of this approach by applying it to the complex Ce-Ni-Si ternarymore » system, whose 17 binary and 21 ternary phases would present a daunting challenge to one seeking to understand the system by manual inspection (but has nonetheless been well-described through the heroic efforts of previous researchers). With the help of PRINCEPS, most of the ternary phases in this system can be rationalized as intergrowths of simple structural fragments, and grouped into a handful of structural series (with some outliers). Lastly, these results illustrate how the PRINCEPS approach can be used to organize a vast collection of crystal structures into structurally meaningful families, and guide the description of complex atomic arrangements.« less

Liquid Crystal Colloids

NASA Astrophysics Data System (ADS)

Smalyukh, Ivan I.

2018-03-01

Colloids are abundant in nature, science, and technology, with examples ranging from milk to quantum dots and the colloidal atom paradigm. Similarly, liquid crystal ordering is important in contexts ranging from biological membranes to laboratory models of cosmic strings and liquid crystal displays in consumer devices. Some of the most exciting recent developments in both of these soft matter fields emerge at their interface, in the fast-growing research arena of liquid crystal colloids. Mesoscale self-assembly in such systems may lead to artificial materials and to structures with emergent physical behavior arising from patterning of molecular order and nano- or microparticles into precisely controlled configurations. Liquid crystal colloids show exceptional promise for new discovery that may impinge on composite material fabrication, low-dimensional topology, photonics, and so on. Starting from physical underpinnings, I review the state of the art in this fast-growing field, with a focus on its scientific and technological potential.

Study of Polymer Crystallization by Physical Vapor Deposition

NASA Astrophysics Data System (ADS)

Jeong, Hyuncheol

When a polymer is confined under the submicron length scale, confinement size and interfaces can significantly impact the crystallization kinetics and resulting morphology. The ability to tune the morphology of confined polymer systems is of critical importance for the development of high-performance polymer microelectronics. The wisdom from the research on confined crystallization suggests that it would be beneficial to have a processing route in which the crystallization of polymers is driven by interface and temperature effects at a nanometer-scale confinement. In practice, for atomic and small-molecular systems, physical vapor deposition (PVD) has been recognized as the most successful processing route for the precise control of the film structure at surface utilizing confinement effects. While standard PVD technologies are not generally applicable to the deposition of the chemically fragile macromolecules, the development of matrix-assisted pulsed laser evaporation (MAPLE) now enables the non-destructive PVD of high-molecular weight polymers. In this thesis work, we investigated the use of MAPLE for the precise control of the crystallization of polymer films at a molecular level. We also sought to decipher the rules governing the crystallization of confined polymers, by using MAPLE as a tool to form confined polymer systems onto substrates with a controlled temperature. We first explored the early stages of film growth and crystallization of poly(ethylene oxide) (PEO) at the substrate surface formed by MAPLE. The unique mechanism of film formation in MAPLE, the deposition of submicron-sized polymer droplets, allowed for the manifestation of confinement and substrate effects in the crystallization of MAPLE-deposited PEO. Furthermore, we also focused on the property of the amorphous PEO film formed by MAPLE, showing the dependence of polymer crystallization kinetics on the thermal history of the amorphous phase. Lastly, we probed how MAPLE processing affected the semi-crystalline structure in MAPLE-deposited polyethylene (PE) films. Depositing PE at various temperatures remarkably allowed for the tunability of the melting temperature and crystallinity of the PE films, thus manipulating the semi-crystalline structure. By comparing the structure of PE formed by different processing routes, i.e., MAPLE and melt-crystallization, we discussed how processing routes affect the development of semi-crystalline phase in polymer films.

TaRh2B2 and NbRh2B2: Superconductors with a chiral noncentrosymmetric crystal structure.

PubMed

Carnicom, Elizabeth M; Xie, Weiwei; Klimczuk, Tomasz; Lin, Jingjing; Górnicka, Karolina; Sobczak, Zuzanna; Ong, Nai Phuan; Cava, Robert J

2018-05-01

It is a fundamental truth in solid compounds that the physical properties follow the symmetry of the crystal structure. Nowhere is the effect of symmetry more pronounced than in the electronic and magnetic properties of materials-even the projection of the bulk crystal symmetry onto different crystal faces is known to have a substantial impact on the surface electronic states. The effect of bulk crystal symmetry on the properties of superconductors is widely appreciated, although its study presents substantial challenges. The effect of a lack of a center of symmetry in a crystal structure, for example, has long been understood to necessitate that the wave function of the collective electron state that gives rise to superconductivity has to be more complex than usual. However, few nonhypothetical materials, if any, have actually been proven to display exotic superconducting properties as a result. We introduce two new superconductors that in addition to having noncentrosymmetric crystal structures also have chiral crystal structures. Because the wave function of electrons in solids is particularly sensitive to the host material's symmetry, crystal structure chirality is expected to have a substantial effect on their superconducting wave functions. Our two experimentally obtained chiral noncentrosymmetric superconducting materials have transition temperatures to superconductivity that are easily experimentally accessible, and our basic property characterization suggests that their superconducting properties may be unusual. We propose that their study may allow for a more in-depth understanding of how chirality influences the properties of superconductors and devices that incorporate them.

Regulation of Silk Material Structure by Temperature-Controlled Water Vapor Annealing

PubMed Central

Hu, Xiao; Shmelev, Karen; Sun, Lin; Gil, Eun-Seok; Park, Sang-Hyug; Cebe, Peggy; Kaplan, David L.

2011-01-01

We present a simple and effective method to obtain refined control of the molecular structure of silk biomaterials through physical temperature-controlled water vapor annealing (TCWVA). The silk materials can be prepared with control of crystallinity, from a low content using conditions at 4°C (alpha-helix dominated silk I structure), to highest content of ~60% crystallinity at 100°C (beta-sheet dominated silk II structure). This new physical approach covers the range of structures previously reported to govern crystallization during the fabrication of silk materials, yet offers a simpler, green chemistry, approach with tight control of reproducibility. The transition kinetics, thermal, mechanical, and biodegradation properties of the silk films prepared at different temperatures were investigated and compared by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), uniaxial tensile studies, and enzymatic degradation studies. The results revealed that this new physical processing method accurately controls structure, in turn providing control of mechanical properties, thermal stability, enzyme degradation rate, and human mesenchymal stem cell interactions. The mechanistic basis for the control is through the temperature controlled regulation of water vapor, to control crystallization. Control of silk structure via TCWVA represents a significant improvement in the fabrication of silk-based biomaterials, where control of structure-property relationships is key to regulating material properties. This new approach to control crystallization also provides an entirely new green approach, avoiding common methods which use organic solvents (methanol, ethanol) or organic acids. The method described here for silk proteins would also be universal for many other structural proteins (and likely other biopolymers), where water controls chain interactions related to material properties. PMID:21425769

Crystal structure of guanidinium hexafluoridovanadate(III), (CN3H6)3[VF6]: an unusual hybrid compound related to perovskite.

PubMed

Black, Cameron; Lightfoot, Philip

2017-03-01

Vanadium fluorides with novel crystal-chemical features and interesting physical properties can be prepared by solvothermal synthetic routes. The title compound, guanidinium hexafluoridovanadate(III), has a cubic structure (space group Pa-3), exhibiting isolated regular VF 6 octahedral units, which are hydrogen bonded to protonated guanidinium moieties. Although the VF 6 octahedral units are not linked directly together, there are structural similarities between this crystal structure and those of the wider family of perovskite materials, in particular, hybrid perovskites based on extended ligands such as cyanide. In this context, the octahedral tilt system of the present compound is of interest and demonstrates that unusual tilt systems can be mediated via `molecular' linkers which allow only supramolecular rather than covalent interactions.

Low-temperature crystal and magnetic structure of α – RuCl 3

DOE PAGES

Cao, Huibo B.; Yan, Jiaqiang; Bridges, Craig A.; ...

2016-04-19

Here, single crystals of the Kitaev spin-liquid candidate α – RuCl 3 have been studied to determine the low-temperature bulk properties, the structure, and the magnetic ground state. Refinements of x-ray diffraction data show that the low-temperature crystal structure is described by space group C2/m with a nearly perfect honeycomb lattice exhibiting less than 0.2% in-plane distortion. The as-grown single crystals exhibit only one sharp magnetic transition at T N = 7 K. The magnetic order below this temperature exhibits a propagation vector of k=(0,1,1/3), which coincides with a three-layer stacking of the C2/m unit cells. Magnetic transitions at highermore » temperatures up to 14 K can be introduced by deformations of the crystal that result in regions in the crystal with a two-layer stacking sequence. The best-fit symmetry-allowed magnetic structure of the as-grown crystals shows that the spins lie in the ac plane, with a zigzag configuration in each honeycomb layer. The three-layer repeat out-of-plane structure can be refined as a 120° spiral order or a collinear structure with a spin direction of 35° away from the a axis. The collinear spin configuration yields a slightly better fit and also is physically preferred. The average ordered moment in either structure is less than 0.45(5) μB per Ru 3+ ion.« less

Physical characteristics of Medicago truncatula calcium oxalate crystals determine their effectiveness in insect defense

USDA-ARS?s Scientific Manuscript database

Plant structural traits can act as defense against herbivorous insects, causing them to avoid feeding on a given plant or tissue. Mineral crystals of calcium oxalate in leaves of Medicago truncatula Gaertn. have previously been shown to be effective deterrents of lepidopteran insect feeding. They ar...

Medicago truncatula-derived calcium oxalate crystals have a negative impact on chewing insect performance via their physical properties

USDA-ARS?s Scientific Manuscript database

Plant structural traits often act as defenses against herbivorous insects, causing them to avoid feeding on a given plant or tissue. Mineral crystals of calcium oxalate in Medicago truncatula Gaertn. (Fabaceae) leaves have previously been shown to be effective deterrents of lepidopteran insect feedi...

Semantic modeling of the structural and process entities during plastic deformation of crystals and rocks

NASA Astrophysics Data System (ADS)

Babaie, Hassan; Davarpanah, Armita

2016-04-01

We are semantically modeling the structural and dynamic process components of the plastic deformation of minerals and rocks in the Plastic Deformation Ontology (PDO). Applying the Ontology of Physics in Biology, the PDO classifies the spatial entities that participate in the diverse processes of plastic deformation into the Physical_Plastic_Deformation_Entity and Nonphysical_Plastic_Deformation_Entity classes. The Material_Physical_Plastic_Deformation_Entity class includes things such as microstructures, lattice defects, atoms, liquid, and grain boundaries, and the Immaterial_Physical_Plastic_Deformation_Entity class includes vacancies in crystals and voids along mineral grain boundaries. The objects under the many subclasses of these classes (e.g., crystal, lattice defect, layering) have spatial parts that are related to each other through taxonomic (e.g., Line_Defect isA Lattice_Defect), structural (mereological, e.g., Twin_Plane partOf Twin), spatial-topological (e.g., Vacancy adjacentTo Atom, Fluid locatedAlong Grain_Boundary), and domain specific (e.g., displaces, Fluid crystallizes Dissolved_Ion, Void existsAlong Grain_Boundary) relationships. The dynamic aspect of the plastic deformation is modeled under the dynamical Process_Entity class that subsumes classes such as Recrystallization and Pressure_Solution that define the flow of energy amongst the physical entities. The values of the dynamical state properties of the physical entities (e.g., Chemical_Potential, Temperature, Particle_Velocity) change while they take part in the deformational processes such as Diffusion and Dislocation_Glide. The process entities have temporal parts (phases) that are related to each other through temporal relations such as precedes, isSubprocessOf, and overlaps. The properties of the physical entities, defined under the Physical_Property class, change as they participate in the plastic deformational processes. The properties are categorized into dynamical, constitutive, spatial, temporal, statistical, and thermodynamical. The dynamical properties, categorized under the Dynamical_Rate_Property and Dynamical_State_Property classes, subsume different classes of properties (e.g., Fluid_Flow_Rate, Temperature, Chemical_Potential, Displacement, Electrical_Charge) based on the physical domain (e.g., fluid, heat, chemical, solid, electrical). The properties are related to the objects under the Physical_Entity class through diverse object type (e.g., physicalPropertyOf) and data type (e.g., Fluid_Pressure unit 'MPa') properties. The changes of the dynamical properties of the physical entities, described by the empirical laws (equations) modeled by experimental structural geologists, are modeled through the Physical_Property_Dependency class that subsumes the more specialized constitutive, kinetic, and thermodynamic expressions of the relationships among the dynamic properties. Annotation based on the PDO will make it possible to integrate and reuse experimental plastic deformation data, knowledge, and simulation models, and conduct semantic-based search of the source data originating from different rock testing laboratories.

Bottom-up photonic crystal approach with top-down defect and heterostructure fine-tuning.

PubMed

Ding, Tao; Song, Kai; Clays, Koen; Tung, Chen-Ho

2010-03-16

We combine the most efficient (chemical) approach toward three-dimensional photonic crystals with the most convenient (physical) technique for creating non-close-packed crystalline structures. Self-assembly of colloidal particles in artificial opals is followed by a carefully tuned plasma etching treatment. By covering the resulting top layer of more open structure with original dense opal, embedded defect layers and heterostructures can be conveniently designed for advanced photonic band gap and band edge engineering.

On the Relationship Between Scintillation Anisotropy and Crystal Structure in Pure Crystalline Organic Scintillator Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schuster, Patricia; Feng, Patrick; Brubaker, Erik

We report the scintillation anisotropy effect for proton recoil events has been investigated in five pure organic crystalline materials: anthracene, trans-stilbene, p-terphenyl, bibenzyl, and diphenylacetylene. These measurements include characterization of the scintillation response for one hemisphere of proton recoil directions in each crystal. In addition to standard measurements of the total light output and pulse shape at each angle, the prompt and delayed light anisotropies are analyzed, allowing for investigation of the singlet and triplet molecular excitation behaviors independently. This work provides new quantitative and qualitative observations that make progress toward understanding the physical mechanisms behind the scintillation anisotropy. Thesemore » measurements show that the relationship between the prompt and delayed light anisotropies is correlated with crystal structure, as it changes between the pi-stacked crystal structure materials (anthracene and p-terphenyl) and the herringbone crystal structure materials (stilbene, bibenzyl, and diphenylacetylene). The observations are consistent with a model in which there are preferred directions of kinetic processes for the molecular excitations. Finally, these processes and the impact of their directional dependencies on the scintillation anisotropy are discussed.« less

On the Relationship Between Scintillation Anisotropy and Crystal Structure in Pure Crystalline Organic Scintillator Materials

DOE PAGES

Schuster, Patricia; Feng, Patrick; Brubaker, Erik

2018-05-03

We report the scintillation anisotropy effect for proton recoil events has been investigated in five pure organic crystalline materials: anthracene, trans-stilbene, p-terphenyl, bibenzyl, and diphenylacetylene. These measurements include characterization of the scintillation response for one hemisphere of proton recoil directions in each crystal. In addition to standard measurements of the total light output and pulse shape at each angle, the prompt and delayed light anisotropies are analyzed, allowing for investigation of the singlet and triplet molecular excitation behaviors independently. This work provides new quantitative and qualitative observations that make progress toward understanding the physical mechanisms behind the scintillation anisotropy. Thesemore » measurements show that the relationship between the prompt and delayed light anisotropies is correlated with crystal structure, as it changes between the pi-stacked crystal structure materials (anthracene and p-terphenyl) and the herringbone crystal structure materials (stilbene, bibenzyl, and diphenylacetylene). The observations are consistent with a model in which there are preferred directions of kinetic processes for the molecular excitations. Finally, these processes and the impact of their directional dependencies on the scintillation anisotropy are discussed.« less

Structure of CPV17 polyhedrin determined by the improved analysis of serial femtosecond crystallographic data

DOE PAGES

Ginn, Helen M.; Messerschmidt, Marc; Ji, Xiaoyun; ...

2015-03-09

The X-ray free-electron laser (XFEL) allows the analysis of small weakly diffracting protein crystals, but has required very many crystals to obtain good data. Here we use an XFEL to determine the room temperature atomic structure for the smallest cytoplasmic polyhedrosis virus polyhedra yet characterized, which we failed to solve at a synchrotron. These protein microcrystals, roughly a micron across, accrue within infected cells. We use a new physical model for XFEL diffraction, which better estimates the experimental signal, delivering a high-resolution XFEL structure (1.75 Å), using fewer crystals than previously required for this resolution. The crystal lattice and proteinmore » core are conserved compared with a polyhedrin with less than 10% sequence identity. We explain how the conserved biological phenotype, the crystal lattice, is maintained in the face of extreme environmental challenge and massive evolutionary divergence. Our improved methods should open up more challenging biological samples to XFEL analysis.« less

The Biophysics Microgravity Initiative

NASA Technical Reports Server (NTRS)

Gorti, S.

2016-01-01

Biophysical microgravity research on the International Space Station using biological materials has been ongoing for several decades. The well-documented substantive effects of long duration microgravity include the facilitation of the assembly of biological macromolecules into large structures, e.g., formation of large protein crystals under micro-gravity. NASA is invested not only in understanding the possible physical mechanisms of crystal growth, but also promoting two flight investigations to determine the influence of µ-gravity on protein crystal quality. In addition to crystal growth, flight investigations to determine the effects of shear on nucleation and subsequent formation of complex structures (e.g., crystals, fibrils, etc.) are also supported. It is now considered that long duration microgravity research aboard the ISS could also make possible the formation of large complex biological and biomimetic materials. Investigations of various materials undergoing complex structure formation in microgravity will not only strengthen NASA science programs, but may also provide invaluable insight towards the construction of large complex tissues, organs, or biomimetic materials on Earth.

Crystal structure and physical properties of a novel Kondo antiferromagnet: U3Ru4Al12

NASA Astrophysics Data System (ADS)

Pasturel, M; Tougait, O; Potel, M; Roisnel, T; Wochowski, K; Noël, H; Troć, R

2009-03-01

A novel ternary compound U3Ru4Al12 has been identified in the U-Ru-Al ternary diagram. Single-crystal x-ray diffraction indicates a hexagonal Gd3Ru4Al12-type structure for this uranium-based intermetallic. While this structure type usually induces geometrically a spin-glass behaviour, an antiferromagnetic ordering is observed at TN = 8.4 K in the present case. The reduced effective magnetic moment of U atoms (μeff = 2.6 µB) can be explained by Kondo-like interactions and crystal field effects that have been identified by a logarithmic temperature dependence of the electrical resistivity, negative values of the magnetoresistivity and particular shape of the Seebeck coefficient.

Glassy nature and glass-to-crystal transition in the binary metallic glass CuZr

NASA Astrophysics Data System (ADS)

Wei, Zi-Yang; Shang, Cheng; Zhang, Xiao-Jie; Liu, Zhi-Pan

2017-06-01

The prediction for the stability of glassy material is a key challenge in physical science. Here, we report a theoretical framework to predict the glass stability based on stochastic surface walking global optimization and reaction pathway sampling. This is demonstrated by revealing for the first time the global potential energy surface (PES) of two systems, CuZr binary metallic glass and nonglassy pure Cu systems, and establishing the lowest energy pathways linking glassy/amorphous structures with crystalline structures. The CuZr system has a significant number of glassy structures on PES that are ˜0.045 eV /atom above the crystal structure. Two clear trends are identified from global PES in the glass-to-crystal transition of the CuZr system: (i) the local Zr-Cu coordination (nearest neighbor) increases, and (ii) the local Zr bonding environment becomes homogeneous. This allows us to introduce quantitative structural and energetics conditions to distinguish the glassy structures from the crystalline structures. Because of the local Zr-Cu exchange in the glass-to-crystal transition, a high reaction barrier (>0.048 eV /atom ) is present to separate the glassy structures and the crystals in CuZr. By contrast, the Cu system, although it does possess amorphous structures that appear at much higher energy (˜0.075 eV /atom ) with respect to the crystal structure, has very low reaction barriers for the crystallization of amorphous structures, i.e. <0.011 eV /atom . The quantitative data on PES now available from global optimization techniques deepens our understanding on the microscopic nature of glassy material and might eventually facilitate the design of stable glassy materials.

Stability of (Fe-Tm-B) amorphous alloys: relaxation and crystallization phenomena

NASA Astrophysics Data System (ADS)

Zemčík, T.

1994-12-01

Fe-Tm-B base (TM=transition metal) amorphous alloys (metallic glasses) are thermodynamically metastable. This limits their use as otherwise favourable materials, e.g. magnetically soft, corrosion resistant and mechanically firm. By analogy of the mechanical strain-stress dependence, at a certain degree of thermal activation the amorphous structure reaches its limiting state where it changes its character and physical properties. Relaxation and early crystallization processes in amorphous alloys, starting already around 100°C, are reviewed involving subsequently stress relief, free volume shrinking, topological and chemical ordering, pre-crystallization phenomena up to partial (primary) crystallization. Two diametrically different examples are demonstrated from among the soft magnetic materials: relaxation and early crystallization processes in the Fe-Co-B metallic glasses and controlled crystallization of amorphous ribbons yielding rather modern nanocrystalline “Finemet” alloys where late relaxation and pre-crystallization phenomena overlap when forming extremely dispersive and fine-grained nanocrystals-in-amorphous-sauce structure. Mössbauer spectroscopy seems to be unique for magnetic and phase analysis of such complicated systems.

Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages

DOE PAGES

Slater, Anna G.; Reiss, Paul S.; Pulido, Angeles; ...

2017-06-20

The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal-organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of a cage molecule, CC3, in a systematic way by introducing methyl groupsmore » into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure-energy landscape of a CC15-R/CC3-S cocrystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy-structure-function maps.« less

Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages

DOE Office of Scientific and Technical Information (OSTI.GOV)

Slater, Anna G.; Reiss, Paul S.; Pulido, Angeles

The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal-organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of a cage molecule, CC3, in a systematic way by introducing methyl groupsmore » into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure-energy landscape of a CC15-R/CC3-S cocrystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy-structure-function maps.« less

Evidence for monoclinic distortion in the ground state phase of underdoped La 1.95Sr 0.05CuO 4: A single crystal neutron diffraction study

DOE PAGES

Singh, Anar; Schefer, Jurg; Sura, Ravi; ...

2016-03-24

The existing controversy about the symmetry of the crystal structure of the ground state of the critical doped La 1.95Sr 0.05CuO 4 has been resolved by analyzing the single crystal neutron diffraction data collected between 5 and 730 K. We observed small but significant intensities for "forbidden" reflections given by extinction rules of the orthorhombic Bmab space group at low temperatures. A careful investigation of neutron diffraction data reveals that the crystal structure of La 1.95Sr 0.05CuO 4 at 5 K is monoclinic with B2/m (2/m 1 1) space group. The monoclinic structure emerges from the orthorhombic structure in amore » continuous way; however, the structure is stable below similar to 120K which agrees with other observed phenomena. Lastly, our results on symmetry changes are crucial for the interpretation of physical properties also in other high temperature superconductors with similar structures.« less

Evidence for monoclinic distortion in the ground state phase of underdoped La{sub 1.95}Sr{sub 0.05}CuO{sub 4}: A single crystal neutron diffraction study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Anar, E-mail: singhanar@gmail.com; Schefer, Jürg; Frontzek, Matthias

2016-03-28

The existing controversy about the symmetry of the crystal structure of the ground state of the critical doped La{sub 1.95}Sr{sub 0.05}CuO{sub 4} has been resolved by analyzing the single crystal neutron diffraction data collected between 5 and 730 K. We observed small but significant intensities for “forbidden” reflections given by extinction rules of the orthorhombic Bmab space group at low temperatures. A careful investigation of neutron diffraction data reveals that the crystal structure of La{sub 1.95}Sr{sub 0.05}CuO{sub 4} at 5 K is monoclinic with B2/m (2/m 1 1) space group. The monoclinic structure emerges from the orthorhombic structure in a continuous way;more » however, the structure is stable below ∼120 K which agrees with other observed phenomena. Our results on symmetry changes are crucial for the interpretation of physical properties also in other high temperature superconductors with similar structures.« less

Liquid Structures and Physical Properties -- Ground Based Studies for ISS Experiments

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Bendert, J. C.; Mauro, N. A.

2012-01-01

Studies of electrostatically-levitated supercooled liquids have demonstrated strong short- and medium-range ordering in transition metal and alloy liquids, which can influence phase transitions like crystal nucleation and the glass transition. The structure is also related to the liquid properties. Planned ISS experiments will allow a deeper investigation of these results as well as the first investigations of a new type of coupling in crystal nucleation in primary crystallizing liquids, resulting from a linking of the stochastic processes of diffusion with interfacial-attachment. A brief description of the techniques used for ground-based studies and some results relevant to planned ISS investigations are discussed.

Monolithic phononic crystals with a surface acoustic band gap from surface phonon-polariton coupling.

PubMed

Yudistira, D; Boes, A; Djafari-Rouhani, B; Pennec, Y; Yeo, L Y; Mitchell, A; Friend, J R

2014-11-21

We theoretically and experimentally demonstrate the existence of complete surface acoustic wave band gaps in surface phonon-polariton phononic crystals, in a completely monolithic structure formed from a two-dimensional honeycomb array of hexagonal shape domain-inverted inclusions in single crystal piezoelectric Z-cut lithium niobate. The band gaps appear at a frequency of about twice the Bragg band gap at the center of the Brillouin zone, formed through phonon-polariton coupling. The structure is mechanically, electromagnetically, and topographically homogeneous, without any physical alteration of the surface, offering an ideal platform for many acoustic wave applications for photonics, phononics, and microfluidics.

Twenty years of molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Cho, A. Y.

1995-05-01

The term "molecular beam epitaxy" (MBE) was first used in one of our crystal growth papers in 1970, after having conducted extensive surface physics studies in the late 1960's of the interaction of atomic and molecular beams with solid surfaces. The unique feature of MBE is the ability to prepare single crystal layers with atomic dimensional precision. MBE sets the standard for epitaxial growth and has made possible semiconductor structures that could not be fabricated with either naturally existing materials or by other crystal growth techniques. MBE led the crystal growth technologies when it prepared the first semiconductor quantum well and superlattice structures that gave unexpected and exciting electrical and optical properties. For example, the discovery of the fractional quantized Hall effect. It brought experimental quantum physics to the classroom, and practically all major universities throughout the world are now equipped with MBE systems. The fundamental principles demonstrated by the MBE growth of III-V compound semiconductors have also been applied to the growth of group IV, II-VI, metal, and insulating materials. For manufacturing, the most important criteria are uniformity, precise control of the device structure, and reproducibility. MBE has produced more lasers (3 to 5 million per month for compact disc application) than any other crystal growth technique in the world. New directions for MBE are to incorporate in-situ, real-time monitoring capabilities so that complex structures can be precisely "engineered". In the future, as environmental concerns increase, the use of toxic arsine and phosphine may be limited. Successful use of valved cracker cells for solid arsenic and phosphorus has already produced InP based injection lasers.

Au133(SPh-tBu)52 Nanomolecules: X-ray Crystallography, Optical, Electrochemical, and Theoretical Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dass, Amala; Theivendran, Shevanuja; Nimmala, Praneeth Reddy

2015-04-15

Crystal structure determination has revolutionized modern science in biology, chemistry, and physics. However, the difficulty in obtaining periodic crystal lattices which are needed for X-ray crystal analysis has hindered the determination of atomic structure in nanomaterials, known as the “nanostructure problem”. Here, by using rigid and bulky ligands, we have overcome this limitation and successfully solved the X-ray crystallographic structure of the largest reported thiolated gold nanomolecule, Au133S52. The total composition, Au133(SPh-tBu)52, was verified using high resolution electrospray ionization mass spectrometry (ESI-MS). The experimental and simulated optical spectra show an emergent surface plasmon resonance that is more pronounced than inmore » the slightly larger Au144(SCH2CH2Ph)60. Theoretical analysis indicates that the presence of rigid and bulky ligands is the key to the successful crystal formation.« less

Au 133 (SPh - t Bu) 52 Nanomolecules: X-ray Crystallography, Optical, Electrochemical, and Theoretical Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dass, Amala; Theivendran, Shevanuja; Nimmala, Praneeth Reddy

2015-04-15

Crystal structure determination has revolutionized modern science in biology, chemistry, and physics. However, the difficulty in obtaining periodic crystal lattices which are needed for X-ray crystal analysis has hindered the determination of atomic structure in nanomaterials, known as the "nanostructure problem". Here, by using rigid and bulky ligands, we have overcome this limitation and successfully solved the X-ray crystallographic structure of the largest reported thiolated gold nanomolecule, Au133S52. The total composition, Au-133(SPh-tBu)(52), was verified using high resolution electrospray ionization mass spectrometry (ESI-MS). The experimental and simulated optical spectra show an emergent surface plasmon resonance that is more pronounced than inmore » the slightly larger Au-144(SCH2CH2Ph)(60). Theoretical analysis indicates that the presence of rigid and bulky ligands is the key to the successful crystal formation.« less

Au133(SPh-tBu)52 nanomolecules: X-ray crystallography, optical, electrochemical, and theoretical analysis.

PubMed

Dass, Amala; Theivendran, Shevanuja; Nimmala, Praneeth Reddy; Kumara, Chanaka; Jupally, Vijay Reddy; Fortunelli, Alessandro; Sementa, Luca; Barcaro, Giovanni; Zuo, Xiaobing; Noll, Bruce C

2015-04-15

Crystal structure determination has revolutionized modern science in biology, chemistry, and physics. However, the difficulty in obtaining periodic crystal lattices which are needed for X-ray crystal analysis has hindered the determination of atomic structure in nanomaterials, known as the "nanostructure problem". Here, by using rigid and bulky ligands, we have overcome this limitation and successfully solved the X-ray crystallographic structure of the largest reported thiolated gold nanomolecule, Au133S52. The total composition, Au133(SPh-tBu)52, was verified using high resolution electrospray ionization mass spectrometry (ESI-MS). The experimental and simulated optical spectra show an emergent surface plasmon resonance that is more pronounced than in the slightly larger Au144(SCH2CH2Ph)60. Theoretical analysis indicates that the presence of rigid and bulky ligands is the key to the successful crystal formation.

Structure of Ordinary Ice Ih. Part 1: Ideal Structure of Ice

DTIC Science & Technology

1993-10-01

T., H . Onuki and R. Onaka (1977) Electronic structures of water and ice. Journal of the Physics Society of Japan, 42: 152-158. Shimaoka, K. (1960...nearest neighbors .................................................................................................................. 5 6. H -bond...8 12. Positions of oxygen atoms in the ice % h crystal

Nondestructive optical testing of the materials surface structure based on liquid crystals

NASA Astrophysics Data System (ADS)

Tomilin, M. G.; Stafeev, S. K.

2011-08-01

Thin layers of nematic liquid crystals (NLCs) may be used as recording media for visualizing structural and microrelief defects, distribution of low power physical fields and modifications of the surface. NLCs are more sensitive in comparison with cholesteric and smectic LCs having super molecular structures. The detecting properties of NLCs are based on local layers deformation, induced by surface fields and observed in polarizing microscope. The structural surface defects or physical field's distribution are dramatically change the distribution of surface tension. Surface defects recording becomes possible if NLC deformed structure is illuminated in transparent or reflective modes and observed in optical polarizing microscope and appearing image is compared with background structure. In this case one observes not the real defect but the local deformation in NLCs. The theory was developed to find out the real size of defects. The resolution of NLC layer is more than 2000 lines/mm. The fields of NLC application are solid crystals symmetry, minerals, metals, semiconductors, polymers and glasses structure inhomogeneities and optical coatings defects detecting. The efficiency of NLC method in biophotonics is illustrated by objective detecting cancer tissues character and visualizing the interaction traces of grippe viruses with antibodies. NLCs may detect solvent components structure in tea, wine and perfume giving unique information of their structure. It presents diagnostic information alternative to dyes and fluorescence methods. For the first time the structures of some juices and beverages are visualized to illustrate the unique possibilities of NLCs.

Microscopic Mechanism of Doping-Induced Kinetically Constrained Crystallization in Phase-Change Materials.

PubMed

Lee, Tae Hoon; Loke, Desmond; Elliott, Stephen R

2015-10-07

A comprehensive microscopic mechanism of doping-induced kinetically constrained crystallization in phase-change materials is provided by investigating structural and dynamical dopant characteristics via ab initio molecular dynamics simulations. The information gained from this study may provide a basis for a fast screening of dopant species for electronic memory devices, or for understanding the general physics involved in the crystallization of doped glasses. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of various applied voltages on physical properties of TiO2 nanotubes by anodization method

NASA Astrophysics Data System (ADS)

Hoseinzadeh, T.; Ghorannevis, Z.; Ghoranneviss, M.; Sari, A. H.; Salem, M. K.

2017-09-01

Three steps anodization process is used to synthesize highly ordered and uniform multilayered titanium oxide (TiO2) nanotubes and effect of different anodization voltages are studied on their physical properties such as structural, morphological and optical. The crystalized structure of the synthesized tubes is investigated by X-ray diffractometer analysis. To study the morphology of the tubes, field emission scanning electron microscopy is used, which showed that the wall thicknesses and the diameters of the tubes are affected by the different anodization voltages. Moreover, optical studies performed by diffuse reflection spectra suggested that band gap of the TiO2 nanotubes are also changed by applying different anodization voltages. In this study using physical investigations, an optimum anodization voltage is obtained to synthesize the uniform crystalized TiO2 nanotubes with suitable diameter, wall thickness and optical properties.

Potassium-cobalt sulphate crystal growth assisted by low frequency vibrations

NASA Astrophysics Data System (ADS)

Sadovsky, A.; Ermochenkov, I.; Dubovenko, E.; Sukhanova, E.; Bebyakin, M.; Dubov, V.; Avetissov, I.

2018-02-01

Single crystals of K2Co(SO4)2·6H2O were grown from solution using the temperature reduction method enhanced by the axial low frequency vibration control technique (AVC-technique). Physical modeling of heat-mass transfer in solution under the AVC action was performed. The growth rate of the AVC grown crystal was found to be twice that of the crystal grown under natural convection conditions. Analysis of spectral characteristics (absorption and Raman spectra) as well as structural properties (dislocation density and microhardness) of the grown crystals showed the significant superiority of the AVC technique for the growth of K2Co(SO4)2·6H2O crystals.

Crystallization of Hard Sphere Colloids in Microgravity: Results of the Colloidal Disorder-Order Transition, CDOT on USML-2. Experiment 33

NASA Technical Reports Server (NTRS)

Zhu, Ji-Xiang; Chaikin, P. M.; Li, Min; Russel, W. B.; Ottewill, R. H.; Rogers, R.; Meyer, W. V.

1998-01-01

Classical hard spheres have long served as a paradigm for our understanding of the structure of liquids, crystals, and glasses and the transitions between these phases. Ground-based experiments have demonstrated that suspensions of uniform polymer colloids are near-ideal physical realizations of hard spheres. However, gravity appears to play a significant and unexpected role in the formation and structure of these colloidal crystals. In the microgravity environment of the Space Shuttle, crystals grow purely via random stacking of hexagonal close-packed planes, lacking any of the face-centered cubic (FCC) component evident in crystals grown in 1 g beyond melting and allowed some time to settle. Gravity also masks 33-539 the natural growth instabilities of the hard sphere crystals which exhibit striking dendritic arms when grown in microgravity. Finally, high volume fraction "glass" samples which fail to crystallize after more than a year in 1 g begin nucleation after several days and fully crystallize in less than 2 weeks on the Space Shuttle.

Studies of Nucleation, Growth, Specific Heat, and Viscosity of Undercooled Melts of Quasicrystals and Polytetrahedral-Phase-Forming Alloys

NASA Technical Reports Server (NTRS)

Kelton, K. F.; Croat, T. K.; Gangopadhyay, A.; Holland-Moritz, D.; Hyers, Robert W.; Rathz, Thomas J.; Robinson, Michael B.; Rogers, Jan R.

2001-01-01

Undercooling experiments and thermal physical property measurements of metallic alloys on the International Space Station (ISS) are planned. This recently-funded research focuses on fundamental issues of the formation and structure of highly-ordered non-crystallographic phases (quasicrystals) and related crystal phases (crystal approximants), and the connections between the atomic structures of these phases and those of liquids and glasses. It extends studies made previously by us of the composition dependence of crystal nucleation processes in silicate and metallic glasses, to the case of nucleation from the liquid phase. Motivating results from rf-levitation and drop-tube measurements of the undercooling of Ti/Zr-based liquids that form quasicrystals and crystal approximants are discussed. Preliminary measurements by electrostatic levitation (ESL) are presented.

Fundamental Studies of Crystal Growth of Microporous Materials

NASA Technical Reports Server (NTRS)

Dutta, P.; George, M.; Ramachandran, N.; Schoeman, B.; Curreri, Peter A. (Technical Monitor)

2002-01-01

Microporous materials are framework structures with well-defined porosity, often of molecular dimensions. Zeolites contain aluminum and silicon atoms in their framework and are the most extensively studied amongst all microporous materials. Framework structures with P, Ga, Fe, Co, Zn, B, Ti and a host of other elements have also been made. Typical synthesis of microporous materials involve mixing the framework elements (or compounds, thereof) in a basic solution, followed by aging in some cases and then heating at elevated temperatures. This process is termed hydrothermal synthesis, and involves complex chemical and physical changes. Because of a limited understanding of this process, most synthesis advancements happen by a trial and error approach. There is considerable interest in understanding the synthesis process at a molecular level with the expectation that eventually new framework structures will be built by design. The basic issues in the microporous materials crystallization process include: (1) Nature of the molecular units responsible for the crystal nuclei formation; (2) Nature of the nuclei and nucleation process; (3) Growth process of the nuclei into crystal; (4) Morphological control and size of the resulting crystal; (5) Surface structure of the resulting crystals; (6) Transformation of frameworks into other frameworks or condensed structures. The NASA-funded research described in this report focuses to varying degrees on all of the above issues and has been described in several publications. Following is the presentation of the highlights of our current research program. The report is divided into five sections: (1) Fundamental aspects of the crystal growth process; (2) Morphological and Surface properties of crystals; (3) Crystal dissolution and transformations; (4) Modeling of Crystal Growth; (5) Relevant Microgravity Experiments.

Crystal Quality, the Long and the Short of It

NASA Technical Reports Server (NTRS)

Snell, Eddie H.

2004-01-01

The term "crystal quality" is ambiguous and implies different meanings to different crystallographers. For the physical crystallographer who aims to understand long-range aspects of crystal growth mosaicity is one of the leading measures of perfection. For the structural crystallographer and those seeking to understand growth at a short-range, molecular level, the detail in the resulting structure is a key goal. Different quality measures have been developed due to different needs. Each of the measures has advantages and each has limitations. In this talk a sample of these measures will be discussed with particular emphasis applied to their application in the analysis of microgravity grown crystals. The advantages and limitations of each will be discussed. Ultimately, the choice of crystal quality measurement lies in the nature of the question asked. It is scfill to remember that beauty is often in the eye of the beholder.

Effect of sintering temperature on physical, structural and optical properties of wollastonite based glass-ceramic derived from waste soda lime silica glasses

NASA Astrophysics Data System (ADS)

Almasri, Karima Amer; Sidek, Hj. Ab Aziz; Matori, Khamirul Amin; Zaid, Mohd Hafiz Mohd

The impact of different sintering temperatures on physical, optical and structural properties of wollastonite (CaSiO3) based glass-ceramics were investigated for its potential application as a building material. Wollastonite based glass-ceramics was provided by a conventional melt-quenching method and followed by a controlled sintering process. In this work, soda lime silica glass waste was utilized as a source of silicon. The chemical composition and physical properties of glass were characterized by using Energy Dispersive X-ray Fluorescence (EDXRF) and Archimedes principle. The Archimedes measurement results show that the density increased with the increasing of sintering temperature. The generation of CaSiO3, morphology, size and crystal phase with increasing the heat-treatment temperature were examined by field emission scanning electron microscopy (FESEM), Fourier transforms infrared reflection spectroscopy (FTIR), and X-ray diffraction (XRD). The average calculated crystal size gained from XRD was found to be in the range 60 nm. The FESEM results show a uniform distribution of particles and the morphology of the wollastonite crystal is in relict shapes. The appearance of CaO, SiO2, and Ca-O-Si bands disclosed from FTIR which showed the formation of CaSiO3 crystal phase. In addition to the calculation of the energy band gap which found to be increased with increasing sintering temperature.

Computed crystal energy landscapes for understanding and predicting organic crystal structures and polymorphism.

PubMed

Price, Sarah Sally L

2009-01-20

The phenomenon of polymorphism, the ability of a molecule to adopt more than one crystal structure, is a well-established property of crystalline solids. The possible variations in physical properties between polymorphs make the reliable reproduction of a crystalline form essential for all research using organic materials, as well as quality control in manufacture. Thus, the last two decades have seen both an increase in interest in polymorphism and the availability of the computer power needed to make the computational prediction of organic crystal structures a practical possibility. In the past decade, researchers have made considerable improvements in the theoretical basis for calculating the sets of structures that are within the energy range of possible polymorphism, called crystal energy landscapes. It is common to find that a molecule has a wide variety of ways of packing with lattice energy within a few kilojoules per mole of the most stable structure. However, as we develop methods to search for and characterize "all" solid forms, it is also now usual for polymorphs and solvates to be found. Thus, the computed crystal energy landscape reflects and to an increasing extent "predicts" the emerging complexity of the solid state observed for many organic molecules. This Account will discuss the ways in which the calculation of the crystal energy landscape of a molecule can be used as a complementary technique to solid form screening for polymorphs. Current methods can predict the known crystal structure, even under "blind test" conditions, but such successes are generally restricted to those structures that are the most stable over a wide range of thermodynamic conditions. The other low-energy structures can be alternative polymorphs, which have sometimes been found in later experimental studies. Examining the computed structures reveals the various compromises between close packing, hydrogen bonding, and pi-pi stacking that can result in energetically feasible structures. Indeed, we have observed that systems with many almost equi-energetic structures that contain a common interchangeable motif correlate with a tendency to disorder and problems with control of the crystallization product. Thus, contrasting the computed crystal energy landscape with the known crystal structures of a given molecule provides a valuable complement to solid form screening, and the examination of the low-energy structures often leads to a rationalization of the forms found.

Search for unconventional superconductors among the YTE 2Si2 compounds (TE  =  Cr, Co, Ni, Rh, Pd, Pt)

NASA Astrophysics Data System (ADS)

Pikul, A. P.; Samsel–Czekała, M.; Chajewski, G.; Romanova, T.; Hackemer, A.; Gorzelniak, R.; Wiśniewski, P.; Kaczorowski, D.

2017-05-01

Motivated by the recent discovery of exotic superconductivity in YFe2Ge2 we undertook reinvestigation of formation and physical properties of yttrium-based 1:2:2 silicides. Here we report on syntheses and crystal structures of the YTE 2Si2 compounds with TE  =  Cr, Co, Ni, Rh, Pd and Pt, and their low-temperature physical properties measurements, supplemented by results of fully relativistic full-potential local-orbital minimum basis band structure calculations. We confirm that most of the members of that family crystallize in a tetragonal ThCr2Si2-type structure (space group I4/mmm) and have three-dimensional Fermi surface, while only one of them (YPt2Si2) forms with a closely-related primitive CaBe2Ge2-type unit cell (space group P4/nmm) and possess quasi-two-dimensional Fermi surface sheets. Physical measurements indicated that BCS-like superconductivity is observed only in YPt2Si2 (T c  =  1.54 K) and YPd2Si2 (T c  =  0.43 K), while no superconducting phase transition was found in other systems at least down to 0.35 K. Thermal analysis showed no polymorphism in both superconducting phases. No clear relation between the superconductivity and the crystal structure (and dimensionality of the Fermi surface) was observed.

Structural features of single crystals of LuB{sub 12} upon a transition to the cage-glass phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolotina, N. B., E-mail: nb-bolotina@mail.ru; Verin, I. A.; Shitsevalova, N. Yu.

2016-03-15

The unit-cell parameters of dodecaboride LuB{sub 12}, which undergoes a transition to the cage-glass phase, have been determined for the first time in the temperature range of 50–75 K by X-ray diffraction, and the single-crystal structure of this compound is established at 50 K. Nonlinear changes in the unit-cell parameters correspond to anomalies in the physical properties near the glass-transition temperature T* ~ 50–70 K. This compound has cubic symmetry at room temperature, and it is reduced to tetragonal symmetry at lower temperatures. Based on the X-ray diffraction data and relying on the physical properties of the crystals, the structuremore » model, in which a small part (~15%) of Lu atoms are displaced from the 2a sites at the centers of the B{sub 24} cuboctahedra to the 16n sites of sp. gr. I4/mmm, seems preferable.« less

Nikolay Kirov Nikolov

NASA Astrophysics Data System (ADS)

Petrov, Minko; Reynolds, Steve

2014-12-01

Professor Nikolay Kirov Nikolov graduated in Chemistry from Sofia University 'St. Kliment Ohridski', Bulgaria, in 1968. He received his Ph.D. degree in 1973, D.Sc. in 1988 and was appointed to the position of Professor of Physics in the Institute of Solid State Physics (ISSP), Bulgarian Academy of Sciences (BAS), in 1989. Prof. Kirov rose to become an international authority in the area of molecular spectroscopy, and in particular in the vibrational spectroscopy of thermotropic liquid crystals. Prof. Kirov was a scientist of high reputation both in Bulgaria and globally. His scientific papers, numbering some 150, focus on the physics of liquid crystals. His systematic investigations of the vibrational spectroscopy of a wide class of thermotropic liquid crystals were collected in the monograph Vibrational spectroscopy of liquid crystals (1984), in which the molecular structure and properties of various liquid crystals, vibrational assignments, orientational order parameters and their calculation by molecular dynamics are presented. A range of liquid crystal materials was categorised and reported in his second book Atlas of vibrational spectra of liquid crystals (1988). Both publications remain a valuable source of information for specialists in the field of molecular spectroscopy. The outstanding contributions and growing reputation of Prof. Kirov led to periods as Visiting Scientist in the Universities of Parma, Calabria and Wroclaw. His abilities as a scientific organizer and leader were also notable, and led to a long and distinguished period of service in the Institute of Solid State Physics, being first appointed in 1980 as Scientific Secretary, and subsequently as Head of the Laboratory of Optics and Spectroscopy (1990-1998) and Director of the Institute (1991-1999). He was Chairman of the Scientific Council of ISSP over this period, and a member of the Specialized Scientific Council on Condensed Matter Physics. Prof. Kirov was a member of the High Testimonial Committee of the Republic of Bulgaria during 1996. Nikolay Kirov was a key figure in the organization, promotion and success of the International School on Condensed Matter Physics (ISCMP), where he was able to use his network of international contacts to excellent effect. He served as Scientific Secretary (1988-1990), Chairman and Editor of the ISCMP Proceedings (1992-1998), and as Chairman Emeritus (2002-2012). Prof. Kirov is an Honorary Member of the Institute of Solid State Physics. He received the Honorary Diploma 'Nicola Obreshkov' in 1986 and the "Marin Drinov" Sign of Honour BAS (on a ribbon) in 1998, for achievements in the physical and mathematical sciences. He was also honoured outside his native Bulgaria, receiving a Gold Medal from Wroclaw University, Poland, in recognition of successful scientific collaborations in the area of molecular structure.

Crystal Ball Replica

NASA Astrophysics Data System (ADS)

Ajamian, John

2016-09-01

The A2 collaboration of the Institute for Nuclear Physics of Johannes Gutenberg University performs research on (multiple) meson photoproduction and nucleon structure and dynamics using a high energy polarized photon beam at specific targets. Particles scattered from the target are detected in the Crystal Ball, or CB. The CB is composed of 672 NaI crystals that surround the target and can analyze particle type and energy of ejected particles. Our project was to create a replica of the CB that could display what was happening in real time on a 3 Dimensional scale replica. Our replica was constructed to help explain the physics to the general public, be used as a tool when calibrating each of the 672 NaI crystals, and to better analyze the electron showering of particles coming from the target. This poster will focus on the hardware steps necessary to construct the replica and wire the 672 programmable LEDS in such a way that they can be mapped to correspond to the Crystal Ball elements. George Washington NSF Grant.

One-dimensional self-confinement promotes polymorph selection in large-area organic semiconductor thin films.

PubMed

Giri, Gaurav; Li, Ruipeng; Smilgies, Detlef-M; Li, Er Qiang; Diao, Ying; Lenn, Kristina M; Chiu, Melanie; Lin, Debora W; Allen, Ranulfo; Reinspach, Julia; Mannsfeld, Stefan C B; Thoroddsen, Sigurdur T; Clancy, Paulette; Bao, Zhenan; Amassian, Aram

2014-04-16

A crystal's structure has significant impact on its resulting biological, physical, optical and electronic properties. In organic electronics, 6,13(bis-triisopropylsilylethynyl)pentacene (TIPS-pentacene), a small-molecule organic semiconductor, adopts metastable polymorphs possessing significantly faster charge transport than the equilibrium crystal when deposited using the solution-shearing method. Here, we use a combination of high-speed polarized optical microscopy, in situ microbeam grazing incidence wide-angle X-ray-scattering and molecular simulations to understand the mechanism behind formation of metastable TIPS-pentacene polymorphs. We observe that thin-film crystallization occurs first at the air-solution interface, and nanoscale vertical spatial confinement of the solution results in formation of metastable polymorphs, a one-dimensional and large-area analogy to crystallization of polymorphs in nanoporous matrices. We demonstrate that metastable polymorphism can be tuned with unprecedented control and produced over large areas by either varying physical confinement conditions or by tuning energetic conditions during crystallization through use of solvent molecules of various sizes.

Structural, chemical and physical properties of pure and La3+ doped L-Threonine acetate crystals

NASA Astrophysics Data System (ADS)

Senthamizhan, A.; Sambathkumar, K.; Nithiyanantham, S.; Venkatachalapathy, M.; Rajkamal, N.

2017-12-01

The pure and La3+ doped L- Threonine crystals can be grown by slow evaporation techniques. The crystal structure were examined through X-Ray diffraction (XRD) analysis, confirmed the P212121 system. The quantitative nature of dopant can be analyzed with Inductively Coupled Plasma (ICP) study. The Fourier Transform Infra-Red (FTIR) and Fourier Transform (FT- Raman) investigations yields the possible stretching/bonding with their functional groups and the qualitative/quantitative nature of both crystals is analyzed. The optical behavior of crystals can be studied through Ultra Violet (UV) - Visible spectrometer. The mechanical, thermal and decomposition studies can be carried out through Vickers hardness test, Thermo Gravometric Analysis (TGA) and Differential Thermal Analysis (DTA). The Non Linear Optical (NLO) properties are found more than Potassium Phosphate (KDP) through Kurtz powders technique. The dielectric and optical absorption studies for both pure and L-doped crystals were studied and interpreted all the properties. The La3+ dopant increases the properties are investigated.

Weyl points and Fermi arcs in a chiral phononic crystal

NASA Astrophysics Data System (ADS)

Li, Feng; Huang, Xueqin; Lu, Jiuyang; Ma, Jiahong; Liu, Zhengyou

2018-01-01

Topological semimetals are materials whose band structure contains touching points that are topologically nontrivial and can host quasiparticle excitations that behave as Dirac or Weyl fermions. These so-called Weyl points not only exist in electronic systems, but can also be found in artificial periodic structures with classical waves, such as electromagnetic waves in photonic crystals and acoustic waves in phononic crystals. Due to the lack of spin and a difficulty in breaking time-reversal symmetry for sound, however, topological acoustic materials cannot be achieved in the same way as electronic or optical systems. And despite many theoretical predictions, experimentally realizing Weyl points in phononic crystals remains challenging. Here, we experimentally realize Weyl points in a chiral phononic crystal system, and demonstrate surface states associated with the Weyl points that are topological in nature, and can host modes that propagate only in one direction. As with their photonic counterparts, chiral phononic crystals bring topological physics to the macroscopic scale.

A novel microseeding method for the crystallization of membrane proteins in lipidic cubic phase.

PubMed

Kolek, Stefan Andrew; Bräuning, Bastian; Stewart, Patrick Douglas Shaw

2016-04-01

Random microseed matrix screening (rMMS), in which seed crystals are added to random crystallization screens, is an important breakthrough in soluble protein crystallization that increases the number of crystallization hits that are available for optimization. This greatly increases the number of soluble protein structures generated every year by typical structural biology laboratories. Inspired by this success, rMMS has been adapted to the crystallization of membrane proteins, making LCP seed stock by scaling up LCP crystallization conditions without changing the physical and chemical parameters that are critical for crystallization. Seed crystals are grown directly in LCP and, as with conventional rMMS, a seeding experiment is combined with an additive experiment. The new method was used with the bacterial integral membrane protein OmpF, and it was found that it increased the number of crystallization hits by almost an order of magnitude: without microseeding one new hit was found, whereas with LCP-rMMS eight new hits were found. It is anticipated that this new method will lead to better diffracting crystals of membrane proteins. A method of generating seed gradients, which allows the LCP seed stock to be diluted and the number of crystals in each LCP bolus to be reduced, if required for optimization, is also demonstrated.

The "Sticky Patch" Model of Crystallization and Modification of Proteins for Enhanced Crystallizability.

PubMed

Derewenda, Zygmunt S; Godzik, Adam

2017-01-01

Crystallization of macromolecules has long been perceived as a stochastic process, which cannot be predicted or controlled. This is consistent with another popular notion that the interactions of molecules within the crystal, i.e., crystal contacts, are essentially random and devoid of specific physicochemical features. In contrast, functionally relevant surfaces, such as oligomerization interfaces and specific protein-protein interaction sites, are under evolutionary pressures so their amino acid composition, structure, and topology are distinct. However, current theoretical and experimental studies are significantly changing our understanding of the nature of crystallization. The increasingly popular "sticky patch" model, derived from soft matter physics, describes crystallization as a process driven by interactions between select, specific surface patches, with properties thermodynamically favorable for cohesive interactions. Independent support for this model comes from various sources including structural studies and bioinformatics. Proteins that are recalcitrant to crystallization can be modified for enhanced crystallizability through chemical or mutational modification of their surface to effectively engineer "sticky patches" which would drive crystallization. Here, we discuss the current state of knowledge of the relationship between the microscopic properties of the target macromolecule and its crystallizability, focusing on the "sticky patch" model. We discuss state-of-the-art in silico methods that evaluate the propensity of a given target protein to form crystals based on these relationships, with the objective to design variants with modified molecular surface properties and enhanced crystallization propensity. We illustrate this discussion with specific cases where these approaches allowed to generate crystals suitable for structural analysis.

Abiotic ligation of DNA oligomers templated by their liquid crystal ordering

NASA Astrophysics Data System (ADS)

Fraccia, Tommaso P.; Smith, Gregory P.; Zanchetta, Giuliano; Paraboschi, Elvezia; Yi, Yougwooo; Walba, David M.; Dieci, Giorgio; Clark, Noel A.; Bellini, Tommaso

2015-03-01

It has been observed that concentrated solutions of short DNA oligomers develop liquid crystal ordering as the result of a hierarchically structured supramolecular self-assembly. In mixtures of oligomers with various degree of complementarity, liquid crystal microdomains are formed via the selective aggregation of those oligomers that have a sufficient degree of duplexing and propensity for physical polymerization. Here we show that such domains act as fluid and permeable microreactors in which the order-stabilized molecular contacts between duplex terminals serve as physical templates for their chemical ligation. In the presence of abiotic condensing agents, liquid crystal ordering markedly enhances ligation efficacy, thereby enhancing its own phase stability. The coupling between order-templated ligation and selectivity provided by supramolecular ordering enables an autocatalytic cycle favouring the growth of DNA chains, up to biologically relevant lengths, from few-base long oligomers. This finding suggests a novel scenario for the abiotic origin of nucleic acids.

Precursor routes to quaternary intermetallics: Synthesis, crystal structure, and physical properties of clathrate-II Cs8Na16Al24Si112

NASA Astrophysics Data System (ADS)

Wei, Kaya; Dong, Yongkwan; Nolas, George S.

2016-05-01

A new quaternary clathrate-II composition, Cs8Na16Al24Si112, was synthesized by kinetically controlled thermal decomposition (KCTD) employing both NaSi and NaAlSi as the precursors and CsCl as a reactive flux. The crystal structure and composition of Cs8Na16Al24Si112 were investigated using both Rietveld refinement and elemental analysis, and the temperature dependent transport properties were investigated. Our results indicate that KCTD with multiple precursors is an effective method for the synthesis of multinary inorganic phases that are not easily accessible by traditional solid-state synthesis or crystal growth techniques.

Liquid crystal devices especially for use in liquid crystal point diffraction interferometer systems

NASA Technical Reports Server (NTRS)

Marshall, Kenneth L. (Inventor)

2009-01-01

Liquid crystal point diffraction interferometer (LCPDI) systems that can provide real-time, phase-shifting interferograms that are useful in the characterization of static optical properties (wavefront aberrations, lensing, or wedge) in optical elements or dynamic, time-resolved events (temperature fluctuations and gradients, motion) in physical systems use improved LCPDI cells that employ a "structured" substrate or substrates in which the structural features are produced by thin film deposition or photo resist processing to provide a diffractive element that is an integral part of the cell substrate(s). The LC material used in the device may be doped with a "contrast-compensated" mixture of positive and negative dichroic dyes.

Liquid crystal devices especially for use in liquid crystal point diffraction interferometer systems

DOEpatents

Marshall, Kenneth L [Rochester, NY

2009-02-17

Liquid crystal point diffraction interferometer (LCPDI) systems that can provide real-time, phase-shifting interferograms that are useful in the characterization of static optical properties (wavefront aberrations, lensing, or wedge) in optical elements or dynamic, time-resolved events (temperature fluctuations and gradients, motion) in physical systems use improved LCPDI cells that employ a "structured" substrate or substrates in which the structural features are produced by thin film deposition or photo resist processing to provide a diffractive element that is an integral part of the cell substrate(s). The LC material used in the device may be doped with a "contrast-compensated" mixture of positive and negative dichroic dyes.

Conformational dynamics of proanthocyanidins: physical and computational approaches

Treesearch

Fred L. Tobiason; Richard W. Hemingway; T. Hatano

1998-01-01

The interaction of plant polyphenols with proteins accounts for a good part of their commercial (e.g., leather manufacture) and biological (e.g., antimicrobial activity) significance. The interplay between observations of physical data such as crystal structure, NMR analyses, and time-resolved fluorescence with results of computational chemistry approaches has been...

Quantum-Mechanical Combinatorial Design of Solids having Target Properties

NASA Astrophysics Data System (ADS)

Zunger, Alex

2007-03-01

(1) One of the most striking aspects of solid state physics is the diversity of structural forms in which crystals appear in Nature. Not only are there many distinct crystal-types, but combinations of two or more crystalline materials (alloys) give rise to various local geometric atomic patters. The already rich repertoire of such forms has recently been significantly enhanced by the advent of artificial crystal growth techniques (MBE, STM- atom positioning, etc.) that can create desired structural forms, such as superlattices and impurity clusters even in defiance of the rules of equilibrium thermodynamics. (2) At the same time, the fields of chemistry of nanostructures and physics of structural phase-transitions have long revealed that different atomic configurations generally lead to different physical properties even without altering the chemical makeup. While the most widely - known illustration of such ``form controls function'' rule is the dramatically different color, conductivity and hardness of the allotropical forms of pure carbon (diamond,graphite, C60), the physics of semiconductor superstructures and nanostructures is full of striking examples of how optical, magnetic and transport properties depend sensitively on atomic configuration. (3) Yet, the history of material research has generally occurred via accidental discoveries of material structures having interesting physical property (semiconductivity, ferromagnetism; superconductivity etc.). This begs the question: can this discovery process be inverted, i.e. can we first articulate a desired target physical property, then search (within a class) for the configuration that has this property? (4) The number of potentially interesting atomic configurations exhibits a combinatorial explosion, so even fast synthesis or fast computations can not survey all. (5) This talk describes the recent steps made by solid state theory + computational physics to address this ``Inverse Design'' (Franceschetti & Zunger, Nature, 402, 60 (1999) problem. I will show how Genetic Algorithms, in combination with efficient (``Order N'') solutions to the Pseudopotential Schrodinger equation allow us to investigate astronomical spaces of atomic configurations in search of the structure with a target physical property. Only a small fraction of all (˜ 10**14 in our case) configurations need to be examined. Physical properties are either calculated on-the-fly (if it's easy), or first ``Cluster-Expanded'' (if the theory is difficult). I will illustrate this Inverse Band Structure approach for (a) Design of required band-gaps in semiconductor superlattices; (b) architecture of impurity --clusters with desired optical properties (PRL 97, 046401, 2006) (c) search for configuration of magnetic ions in semiconductors that maximize the ferromagnetic Curie temperature (PRL, 97, 047202, 2006).

Structure and Dynamics of Freely Suspended Liquid Crystals

NASA Technical Reports Server (NTRS)

Clark, Noel A.

2004-01-01

Smectic liquid crystals are phases of rod shaped molecules organized into one dimensionally (1 D) periodic arrays of layers, each layer being between one and two molecular lengths thick. In the least ordered smectic phases, the smectics A and C, each layer is a two dimensional (2D) liquid. Additionally there are a variety of more ordered smectic phases having hexatic short range translational order or 2D crystalline or quasi long range translational order within the layers. The inherent fluid-layer structure and low vapor pressure of smectic liquid crystals enables the long term stabilization of freely suspended, single component, layered fluid films as thin as 30A, a single molecular layer. The layering forces the films to be an integral number of smectic layers thick, quantizing their thickness in layer units and forcing a film of a particular number of layers to be physically homogeneous with respect to its layer structure over its entire area. Optical reflectivity enables the precise determination of the number of layers. These ultrathin freely suspended liquid crystal films are structures of fundamental interest in condensed matter and fluid physics. They are the thinnest known stable fluid structures and have the largest surface-to-volume ratio of any stable fluid preparation, making them ideal for the study of the effects of reduced dimensionality on phase behavior and on fluctuation and interface phenomena. Their low vapor pressure and quantized thickness enable the effective use of microgravity to extend the study of basic capillary phenomena to ultrathin fluid films. Freely suspended films have been a wellspring of new LC physics. They have been used to provide unique experimental conditions for the study of condensed phase transitions in two dimensions. They are the only system in which the hexatic has been unambiguously identified as a phase of matter, and the only physical system in which fluctuations of a 2D XY system and Kosterlitz Thouless phase transition has been observed and 2D XY quasi long range order verified. Smectic films have enabled the precise determination of smectic layer electron density and positional fluctuation profiles and have been used to show that the interlayer interactions in antiferroelectric tilted smectics do not extend significantly beyond nearest neighbors. Freely suspended films played a pivotal role in the recent discovery of macroscopic chiral-polar ordering in fluids of achiral molecules. The interactions which are operative in liquid crystals are generally weak in comparison to those in crystalline phases, leading to the facile manipulation of the order in liquid crystals by external agents such as applied fields and surfaces. Effects arising from weak ordering are significantly enhanced in ultrathin free films and filaments, in which the intermolecular coupling is effectively further reduced by loss of neighbors. Over the past four years this research, which we now detail, has produced a host of exciting new discoveries and unexpected results, maintaining the study of freely suspended liquid crystal structures as one of most exciting and fruitful areas of complex fluid physics. In addition, a class of experiments on the behavior of 1D interfaces in 2D films have been pursued with results that point to potentially quite interesting effects in microgravity.

PRINCEPS: A computer-based approach to the structural description and recognition of trends within structural databases, and its application to the Ce-Ni-Si System

DOE PAGES

Guo, Yiming; Fredrickson, Daniel C.

2016-04-01

Intermetallic crystal structures offer an enormous structural diversity, with an endless array of structural motifs whose connection to stability and physical properties are often mysterious. Making sense of the often complex crystal structures that arise here, developing a clear structural description, and identifying connections to other phases can be laborious and require an encyclopedic knowledge of structure types. In this Article, we present PRINCEPS, an algorithm based on a new coordination environment projection scheme that facilitates the structural analysis and comparison of such crystal structures. We demonstrate the potential of this approach by applying it to the complex Ce-Ni-Si ternarymore » system, whose 17 binary and 21 ternary phases would present a daunting challenge to one seeking to understand the system by manual inspection (but has nonetheless been well-described through the heroic efforts of previous researchers). With the help of PRINCEPS, most of the ternary phases in this system can be rationalized as intergrowths of simple structural fragments, and grouped into a handful of structural series (with some outliers). Lastly, these results illustrate how the PRINCEPS approach can be used to organize a vast collection of crystal structures into structurally meaningful families, and guide the description of complex atomic arrangements.« less

Thermo-optic characteristics and switching power limit of slow-light photonic crystal structures on a silicon-on-insulator platform.

PubMed

Chahal, Manjit; Celler, George K; Jaluria, Yogesh; Jiang, Wei

2012-02-13

Employing a semi-analytic approach, we study the influence of key structural and optical parameters on the thermo-optic characteristics of photonic crystal waveguide (PCW) structures on a silicon-on-insulator (SOI) platform. The power consumption and spatial temperature profile of such structures are given as explicit functions of various structural, thermal and optical parameters, offering physical insight not available in finite-element simulations. Agreement with finite-element simulations and experiments is demonstrated. Thermal enhancement of the air-bridge structure is analyzed. The practical limit of thermo-optic switching power in slow light PCWs is discussed, and the scaling with key parameters is analyzed. Optical switching with sub-milliwatt power is shown viable.

Crystal and Magnetic Structures in Layered, Transition Metal Dihalides and Trihalides

DOE PAGES

McGuire, Michael A.

2017-04-27

Materials composed of two dimensional layers bonded to one another through weak van der Waals interactions often exhibit strongly anisotropic behaviors and can be cleaved into very thin specimens and sometimes into monolayer crystals. Interest in such materials is driven by the study of low dimensional physics and the design of functional heterostructures. Binary compounds with the compositions MX 2 and MX 3 where M is a metal cation and X is a halogen anion often form such structures. Magnetism can be incorporated by choosing a transition metal with a partially filled d-shell for M, enabling ferroic responses for enhancedmore » functionality. Here we give a brief overview of binary transition metal dihalides and trihalides, summarizing their crystallographic properties and long-range-ordered magnetic structures, focusing on those materials with layered crystal structures and partially filled d-shells required for combining low dimensionality and cleavability with magnetism.« less

Structural, mechanical, and magnetic properties of ferrite-austenite mixture in evaporated 304 stainless steel thin films

NASA Astrophysics Data System (ADS)

Merakeb, Noureddine; Messai, Amel; Djelloul, Abdelkader; Ayesh, Ahmad I.

2015-11-01

In this paper, we investigate the structure, composition, magnetic, and mechanical properties of stainless steel thin films formed by thermal evaporation technique. These thin films reveal novel structural and physical properties where they were found to consist of nanocrystals that are ~90 % body-centred cubic crystal structure which holds ferromagnetic properties (α-phase), and ~10 % face-centred cubic crystal structure which is paramagnetic at room temperature (γ-phase). The presence of the above phases was quantified by X-ray diffraction, transmission electron microscopy, and conversion electron Mössbauer spectroscopy. The magnetic properties were evaluated by a superconducting quantum interference device magnetometer, and they confirmed the dual-phase crystal structure of the stainless thin films, where the presence of γ-phase reduced the magnetization of the produced thin films. In addition, the fabricated stainless steel thin films did not contain micro-cracks, and they exhibit a tensile stress of about 1.7 GPa, hardness of 7.5 GPa, and elastic modulus of 104 GPa.

The use of polyoxometalates in protein crystallography – An attempt to widen a well-known bottleneck

PubMed Central

Bijelic, Aleksandar; Rompel, Annette

2015-01-01

Polyoxometalates (POMs) are discrete polynuclear metal-oxo anions with a fascinating variety of structures and unique chemical and physical properties. Their application in various fields is well covered in the literature, however little information about their usage in protein crystallization is available. This review summarizes the impact of the vast class of POMs on the formation of protein crystals, a well-known (frustrating) bottleneck in macromolecular crystallography, with the associated structure elucidation and a particular emphasis focused on POM's potential as a powerful crystallization additive for future research. The Protein Data Bank (PDB) was scanned for protein structures with incorporated POMs which were assigned a PDB ligand ID resulting in 30 PDB entries. These structures have been analyzed with regard to (i) the structure of POM itself in the immediate protein environment, (ii) the kind of interaction and position of the POM within the protein structure and (iii) the beneficial effects of POM on protein crystallography apparent so far. PMID:26339074

Fluid Physics and Macromolecular Crystal Growth in Microgravity

NASA Technical Reports Server (NTRS)

Helliwell, John R.; Snell, Edward H.; Chayen, Naomi E.; Judge, Russell A.; Boggon, Titus J.; Pusey, M. L.; Rose, M. Franklin (Technical Monitor)

2000-01-01

The first protein crystallization experiment in microgravity was launched in April, 1981 and used Germany's Technologische Experimente unter Schwerelosigkeit (TEXUS 3) sounding rocket. The protein P-galactosidase (molecular weight 465Kda) was chosen as the sample with a liquid-liquid diffusion growth method. A sliding device brought the protein, buffer and salt solution into contact when microgravity was reached. The sounding rocket gave six minutes of microgravity time with a cine camera and schlieren optics used to monitor the experiment, a single growth cell. In microgravity a strictly laminar diffusion process was observed in contrast to the turbulent convection seen on the ground. Several single crystals, approx 100micron in length, were formed in the flight which were of inferior but of comparable visual quality to those grown on the ground over several days. A second experiment using the same protocol but with solutions cooled to -8C (kept liquid with glycerol antifreeze) again showed laminar diffusion. The science of macromolecular structural crystallography involves crystallization of the macromolecule followed by use of the crystal for X-ray diffraction experiments to determine the three dimensional structure of the macromolecule. Neutron protein crystallography is employed for elucidation of H/D exchange and for improved definition of the bound solvent (D20). The structural information enables an understanding of how the molecule functions with important potential for rational drug design, improved efficiency of industrial enzymes and agricultural chemical development. The removal of turbulent convection and sedimentation in microgravity, and the assumption that higher quality crystals will be produced, has given rise to the growing number of crystallization experiments now flown. Many experiments can be flown in a small volume with simple, largely automated, equipment - an ideal combination for a microgravity experiment. The term "protein crystal growth" is often historically used to describe these microgravity experiments. This is somewhat inaccurate as the field involves the study of many varied biological molecules including viruses, proteins, DNA, RNA and complexes of those structures. For this reason we use the term macromolecular crystal growth. In this chapter we review a series of diagnostic microgravity crystal growth experiments carried out principally using the European Space Agency (ESA) Advanced Protein Crystallization Facility (APCF). We also review related research, both experimental and theoretical, on the aspects of microgravity fluid physics that affect microgravity protein crystal growth. Our experiments have revealed some surprises that were not initially expected. We discuss them here in the context of practical lessons learnt and how to maximize the limited microgravity opportunities available.

Crystal Engineering; How molecules build solids

NASA Astrophysics Data System (ADS)

Williams, Jeffrey H.

2017-09-01

There are more than 20 million chemicals in the literature, with new materials being synthesized each week. Most of these molecules are stable, and the 3-dimensional arrangement of the atoms in the molecules, in the various solids may be determined by routine x-ray crystallography. When this is done, it is found that this vast range of molecules, with varying sizes and shapes can be accommodated by only a handful of solid structures. This limited number of architectures for the packing of molecules of all shapes and sizes, to maximize attractive intermolecular forces and minimizing repulsive intermolecular forces, allows us to develop simple models of what holds the molecules together in the solid. In this volume we look at the origin of the molecular architecture of crystals; a topic that is becoming increasingly important and is often termed, crystal engineering. Such studies are a means of predicting crystal structures, and of designing crystals with particular properties by manipulating the structure and interaction of large molecules. That is, creating new crystal architectures with desired physical characteristics in which the molecules pack together in particular architectures; a subject of particular interest to the pharmaceutical industry.

Iron vacancy in tetragonal Fe1-xS crystals and its effect on the structure and superconductivity.

PubMed

Guo, Zhongnan; Sun, Fun; Han, Bingling; Lin, Kun; Zhou, Liang; Yuan, Wenxia

2017-03-29

Understanding the effects of non-stoichiometry on the structure and physical properties of tetragonal Fe chalcogenides is of great importance, especially for developing fascinating superconductivity in this system, which might be very sensitive to the non-stoichiometry. In this study, a series of Fe 1-x S single crystals were synthesized by a hydrothermal method, which show varying concentrations of Fe vacancies (0 ≤ x ≤ 0.1) in the structure. Based on the crystal samples, the effects of vacancies on the crystal structure and physical properties were studied. The vacancy-free sample (x = 0) showed a metallic state in resistance and superconductivity below 4.5 K, whereas for the samples with Fe vacancies (x ≥ 0.05), the SC was degraded and the sample exhibited semiconducting behavior. Structural analysis showed that the Fe vacancy decreases the lattice parameter a, but elongates c, leading to enhanced tetragonality in Fe 1-x S. Selected-area electron diffraction showed that the vacancy in Fe 1-x S was disordered, which is different from the scenario in FeSe-based materials. On combining the abovementioned results with the first-principles calculations, it was speculated that the disappearance of SC in non-stoichiometric Fe 1-x S resulted from the localization of the 3d electrons of Fe. Moreover, the accompanied metal-insulator transition induced by Fe vacancy mainly belonged to the Mott mechanism because the vacancy did not significantly alter the band structure. These results not only provide deep insight into the effect of Fe vacancy in Fe chalcogenides, but also provide a basis to effectively induce SC in Fe sulfides by decreasing the number of Fe vacancies.

Role of Solvents in Improvement of Dissolution Rate of Drugs: Crystal Habit and Crystal Agglomeration

PubMed Central

Maghsoodi, Maryam

2015-01-01

Crystallization is often used for manufacturing drug substances. Advances of crystallization have achieved control over drug identity and purity, but control over the physical form remains poor. This review discusses the influence of solvents used in crystallization process on crystal habit and agglomeration of crystals with potential implication for dissolution. According to literature it has been known that habit modification of crystals by use of proper solvents may enhance the dissolution properties by changing the size, number and the nature of crystal faces exposed to the dissolution medium. Also, the faster dissolution rate of drug from the agglomerates of crystals compared with the single crystals may be related to porous structure of the agglomerates and consequently their better wettability. It is concluded from this review that in-depth understanding of role of the solvents in crystallization process can be applied to engineering of crystal habit or crystal agglomeration, and predictably dissolution improvement in poorly soluble drugs. PMID:25789214

Processing of mercurous chloride in reduced gravity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watson, C.; Singh, N.; Thomas, A.

1996-12-31

In a joint experiment between the Northrop-Grumman Science and Technology Center and the University of Alabama in Huntsville, Consortium for Materials Development in Space (UAH/CMDS), single crystals of mercurous chloride (Hg{sub 2}Cl{sub 2}) were grown in the Space Experiment Facility (SEF) transparent furnace that was flown on Spacelab 4 (STS-77) in May 1996. Single crystals of this material can be readily grown in normal gravity by closed-tube physical vapor transport, but the crystals generally contain structural inhomogeneities which degrade the optical performance. The nature and cause of these defects are not completely understood, but their degree appears to correlate withmore » the Rayleigh number that characterizes the convective transport during their growth; hence, it is suspected that uncontrolled convection may play a role in the defect structure. The objective of the flight experiment was to reduce the convective flows by several orders of magnitude to see if the structural inhomogeneities can be reduced or eliminated. This paper will describe the physical and thermal properties of the SEF furnace, the ampoule design and loading procedure, and the ground testing, and will also present the preliminary flight results.« less

Defect related electrical and optical properties of AlN bulk crystals grown by physical vapor transport

NASA Astrophysics Data System (ADS)

Irmscher, Klaus

AlN crystallizes thermodynamically stable in the wurtzite structure and possesses a direct band gap of about 6 eV. It is the ideal substrate for the epitaxial growth of Al-rich AlxGa1-xN films that enable deep ultraviolet (UV) emitters. Appropriate AlN bulk crystals can be grown by physical vapor transport (PVT). Besides high structural perfection, such substrate crystals should be highly UV transparent and ideally, electrically conductive. It is well known that point defects like impurities and intrinsic defects may introduce electronic energy levels within the bandgap, which lead to additional optical absorption or electrical compensation. Among the impurities, which may be incorporated into the AlN crystals during PVT growth at well above 2000 ° C, oxygen, carbon, and silicon play the major role. Based on our own experimental data as well as on experimental and theoretical results reported in literature, we discuss energy levels, charge states and possible negative-U behavior of these impurities and of vacancy-type defects. In particular, we develop a model that explains the absorption behavior of the crystals in dependence on the Fermi level that can be controlled by the growth conditions, including intentional doping. Further, we pay attention on spectroscopic investigations giving direct evidence for the chemical nature and atomic arrangement of the involved point defects. As examples local vibrational mode (LVM) spectroscopy of carbon related defects and recent reports of electron paramagnetic resonance (EPR) spectroscopy are discussed.

Distribution function of random strains in an elastically anisotropic continuum and defect strengths of T m3 + impurity ions in crystals with zircon structure

NASA Astrophysics Data System (ADS)

Malkin, B. Z.; Abishev, N. M.; Baibekov, E. I.; Pytalev, D. S.; Boldyrev, K. N.; Popova, M. N.; Bettinelli, M.

2017-07-01

We construct a distribution function of the strain-tensor components induced by point defects in an elastically anisotropic continuum, which can be used to account quantitatively for many effects observed in different branches of condensed matter physics. Parameters of the derived six-dimensional generalized Lorentz distribution are expressed through the integrals computed over the array of strains. The distribution functions for the cubic diamond and elpasolite crystals and tetragonal crystals with the zircon and scheelite structures are presented. Our theoretical approach is supported by a successful modeling of specific line shapes of singlet-doublet transitions of the T m3 + ions doped into AB O4 (A =Y , Lu; B =P , V) crystals with zircon structure, observed in high-resolution optical spectra. The values of the defect strengths of impurity T m3 + ions in the oxygen surroundings, obtained as a result of this modeling, can be used in future studies of random strains in different rare-earth oxides.

What did Erwin mean? The physics of information from the materials genomics of aperiodic crystals and water to molecular information catalysts and life.

PubMed

Varn, D P; Crutchfield, J P

2016-03-13

Erwin Schrödinger famously and presciently ascribed the vehicle transmitting the hereditary information underlying life to an 'aperiodic crystal'. We compare and contrast this, only later discovered to be stored in the linear biomolecule DNA, with the information-bearing, layered quasi-one-dimensional materials investigated by the emerging field of chaotic crystallography. Despite differences in functionality, the same information measures capture structure and novelty in both, suggesting an intimate coherence between the information character of biotic and abiotic matter-a broadly applicable physics of information. We review layered solids and consider three examples of how information- and computation-theoretic techniques are being applied to understand their structure. In particular, (i) we review recent efforts to apply new kinds of information measures to quantify disordered crystals; (ii) we discuss the structure of ice I in information-theoretic terms; and (iii) we recount recent investigations into the structure of tris(bicyclo[2.1.1]hexeno)benzene, showing how an information-theoretic analysis yields additional insight into its structure. We then illustrate a new Second Law of Thermodynamics that describes information processing in active low-dimensional materials, reviewing Maxwell's Demon and a new class of molecular devices that act as information catalysts. Lastly, we conclude by speculating on how these ideas from informational materials science may impact biology. © 2016 The Author(s).

Identification of surface domain structure on enamel crystals using polyamidoamine dendrimer

NASA Astrophysics Data System (ADS)

Chen, Haifeng; Clarkson, Brian H.; Orr, Bradford; Majoros, Istvan; Banaszak Holl, Mark M.

2002-03-01

The control of hydroxyapatite crystal nucleation and crystal growth is central to the mineralization and remineralization of enamel and dentin of teeth. However, the precise biomolecular mechanisms involved remain obscure. The intimate association between the crystal's surface and extracellular protein components implies a modulating role for organic crystal interactions probably mediated via specific crystal surface domains. These include lattice defects and specific stereochemical arrays on associated organic molecules. The nature of protein-crystal interaction depends upon the physical forces of attraction / repulsion between specific biomolecular groups and crystal surface domains. The proposed study is to utilize specific polyamidoamine (PAMAM) dendrimers, also known as “artificial proteins”, acting as nanoprobe. These will be used to probe specific surface domain on the surface of the naturally derived crystals of hydroxyapatite and to determine how control of growth and dissolution may be affected at the biomolecular level. The hydroxyapatite crystals are extracted from the maturation stage enamel of rats. Three types of PAMAM dendrimers, respectively with amine-, carboxylic acid and methyl-capped surface, will be applied in the study. The dendrimer binding on the surface of the hydoxyapatite crystals will be characterized using atomic force microscopy (AFM). The different dendrimer binding on the crystals will disclose the specific surface domain structure on the crystals, which is assumed to be important in binding the extracellular protein.

Genarris: Random generation of molecular crystal structures and fast screening with a Harris approximation

NASA Astrophysics Data System (ADS)

Li, Xiayue; Curtis, Farren S.; Rose, Timothy; Schober, Christoph; Vazquez-Mayagoitia, Alvaro; Reuter, Karsten; Oberhofer, Harald; Marom, Noa

2018-06-01

We present Genarris, a Python package that performs configuration space screening for molecular crystals of rigid molecules by random sampling with physical constraints. For fast energy evaluations, Genarris employs a Harris approximation, whereby the total density of a molecular crystal is constructed via superposition of single molecule densities. Dispersion-inclusive density functional theory is then used for the Harris density without performing a self-consistency cycle. Genarris uses machine learning for clustering, based on a relative coordinate descriptor developed specifically for molecular crystals, which is shown to be robust in identifying packing motif similarity. In addition to random structure generation, Genarris offers three workflows based on different sequences of successive clustering and selection steps: the "Rigorous" workflow is an exhaustive exploration of the potential energy landscape, the "Energy" workflow produces a set of low energy structures, and the "Diverse" workflow produces a maximally diverse set of structures. The latter is recommended for generating initial populations for genetic algorithms. Here, the implementation of Genarris is reported and its application is demonstrated for three test cases.

Studies on 2-amino-5-nitropyridinium nitrate (2A5NPN): A semi-organic third order nonlinear optical single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sivasubramani, V.; Pandian, Muthu Senthil, E-mail: senthilpandianm@ssn.edu.in; Ramasamy, P.

2016-05-23

2-amino-5-nitropyridinium nitrate (2A5NPN) is a semi-organic nonlinear optical crystal and optically good quality 2A5NPN single crystals were successfully grown by slow evaporation solution growth technique (SEST) at ambient temperature. The crystallographic structure of the grown crystal was determined by single crystal X-Ray diffraction analysis and it belongs to Monoclinic crystal system with centro symmetric crystalline nature. The crystallinity of the grown crystal was confirmed by powder X-ray diffraction analysis. The other physical properties of grown crystals are also characterized using TG-DTA, UV-Visible NIR, chemical etching, photoconductivity and Z-scan measurements. The Z-scan method reveals that the 2A5NPN crystal possesses multi photonmore » absorption behaviour and the significantly higher third order susceptibility and it is a promising potential NLO material.« less

Effects of Pressure-shift Freezing on the Structural and Physical Properties of Gelatin Hydrogel Matrices

PubMed Central

Kim, Byeongsoo; Gil, Hyung Bae; Min, Sang-Gi; Lee, Si-Kyung; Choi, Mi-Jung

2014-01-01

This study investigates the effects of the gelatin concentration (10-40%, w/v), freezing temperatures (from -20℃ to -50℃) and freezing methods on the structural and physical properties of gelatin matrices. To freeze gelatin, the pressure-shift freezing (PSF) is being applied at 0.1 (under atmospheric control), 50 and 100 MPa, respectively. The freezing point of gelatin solutions decrease with increasing gelatin concentrations, from -0.2℃ (10% gelatin) to -6.7℃ (40% gelatin), while the extent of supercooling did not show any specific trends. The rheological properties of the gelatin indicate that both the storage (G') and loss (G") moduli were steady in the strain amplitude range of 0.1-10%. To characterize gelatin matrices formed by the various freezing methods, the ice crystal sizes which were being determined by the scanning electron microscopy (SEM) are affected by the gelatin concentrations. The ice crystal sizes are affected by gelatin concentrations and freezing temperature, while the size distributions of ice crystals depend on the freezing methods. Smaller ice crystals are being formed with PSF rather than under the atmospheric control where the freezing temperature is above -40℃. Thus, the results of this study indicate that the PSF processing at a very low freezing temperature (-50℃) offers a potential advantage over commercial atmospheric freezing points for the formation of small ice crystals. PMID:26760743

Electronic and crystal structure changes induced by in-plane oxygen vacancies in multiferroic YMnO 3

DOE PAGES

Cheng, Shaobo; Meng, Qingping; Li, Mengli; ...

2016-02-08

Here, the widely spread oxygen vacancies (V O) in multiferroic materials can strongly affect their physical properties. However, their exact influence has rarely been identified in hexagonal manganites. Here, with the combined use of transmission electron microscopy (TEM) and first-principles calculations, we have systematically studied the electronic and crystal structure modifications induced by V O located at the same Mn atomic plane (in-plane V O). Our TEM experiments reveal that the easily formed in-plane V O not only influence the electronic structure of YMnO 3 but alter the in-plane Wyckoff positions of Mn ions, which may subsequently affect the intraplanemore » and interplane exchange interaction of Mn ions. The ferroelectricity is also impaired due to the introduction of V O. Further calculations confirm these electronic and structural changes and modifications. Our results indicate that the electronic and crystal structure of YMnO 3 can be manipulated by the creation of V O.« less

The ‘Sticky Patch’ Model of Crystallization and Modification of Proteins for Enhanced Crystallizability

PubMed Central

Derewenda, Zygmunt S.; Godzik, Adam

2017-01-01

Crystallization of macromolecules has long been perceived as a stochastic process, which cannot be predicted or controlled. This is consistent with another popular notion that the interactions of molecules within the crystal, i.e. crystal contacts, are essentially random and devoid of specific physicochemical features. In contrast, functionally relevant surfaces, such as oligomerization interfaces and specific protein-protein interaction sites, are under evolutionary pressures so their amino acid composition, structure and topology are distinct. However, current theoretical and experimental studies are significantly changing our understanding of the nature of crystallization. The increasingly popular ‘sticky patch’ model, derived from soft matter physics, describes crystallization as a process driven by interactions between select, specific surface patches, with properties thermodynamically favorable for cohesive interactions. Independent support for this model comes from various sources including structural studies and bioinformatics. Proteins that are recalcitrant to crystallization can be modified for enhanced crystallizability through chemical or mutational modification of their surface to effectively engineer ‘sticky patches’ which would drive crystallization. Here, we discuss the current state of knowledge of the relationship between the microscopic properties of the target macromolecule and its crystallizability, focusing on the ‘sticky patch’ model. We discuss state-of-art in silico methods that evaluate the propensity of a given target protein to form crystals based on these relationships, with the objective to design of variants with modified molecular surface properties and enhanced crystallization propensity. We illustrate this discussion with specific cases where these approaches allowed to generate crystals suitable for structural analysis. PMID:28573570

Physical stability enhancement of theophylline via cocrystallization.

PubMed

Trask, Andrew V; Motherwell, W D Sam; Jones, William

2006-08-31

The crystal form adopted by the respiratory drug theophylline was modified using a crystal engineering strategy in order to search for a solid material with improved physical stability. Cocrystals, also referred to as crystalline molecular complexes, were prepared with theophylline and one of several dicarboxylic acids. Four cocrystals of theophylline are reported, one each with oxalic, malonic, maleic and glutaric acids. Crystal structures were obtained for each cocrystal material, allowing an examination of the hydrogen bonding and crystal packing features. The cocrystal design scheme was partly based upon a series of recently reported cocrystals of the molecular analogue, caffeine, and comparisons in packing features are drawn between the two cocrystal series. The theophylline cocrystals were subjected to relative humidity challenges in order to assess their stability in relation to crystalline theophylline anhydrate and the equivalent caffeine cocrystals. None of the cocrystals in this study converted into a hydrated cocrystal upon storage at high relative humidity. Furthermore, the theophylline:oxalic acid cocrystal demonstrated superior humidity stability to theophylline anhydrate under the conditions examined, while the other cocrystals appeared to offer comparable stability to that of theophylline anhydrate. The results demonstrate the feasibility of pharmaceutical cocrystal design based upon the crystallization preferences of a molecular analogue, and furthermore show that avoidance of hydrate formation and improvement in physical stability is possible via pharmaceutical cocrystallization.

Statistical physics of modulated phases in nematic liquid crystals

NASA Astrophysics Data System (ADS)

Shamid, Shaikh M.

Nematic liquid crystals are the state of the matter in which there is no positional order like crystals but it has orientational order of the constituent molecules. In the conventional nematics, the long axes of the rod-like molecules tend to align up or down uniformly along a director n. If the constituent molecules are chiral, they tend to form a modulated structure in one of the space dimensions. They are called the chiral nematics. If the chirality is strong enough we get the modulated structures in all three dimensions called the chiral blue phase. On the other hand, if the molecules are achiral, but an additional polar dipole is attached to the molecules, they also tend to form a modulated structure. In these types of materials we observe an important physical effect called flexoelectric effect, in which the polar order is linearly coupled to the director gradients. This dissertation work presents analytical and simulation studies of that modulated structures using the flexoelectric mechanism. Classic work by R. B. Meyer and further studies by I. Dozov predicted two possible structures, known as twist-bend and splay-bend. One of these predictions, the twist-bend phase, has recently been identified in experiments on bent-shaped liquid crystals. In this recently discovered twist-bend nematic phase the modulation is along one of the space dimensions. If this flexoelectric coupling is strong enough, in addition to twist-bend and splay-bend, here we predict the formation of polar analog of chiral blue phases (in both 2D and 3D) made of achiral polar liquid crystal materials by using Elastic continuum theory-based numerical calculations and computer simulations. This dissertation work also presents the coarse-grained theory of twist-bend phase. This theory predicts normal modes of fluctuation in both sides of nematic to twist-bend transition, which then compared with light scattering experiments. Macroscopic elastic and electric properties of twist-bend nematics can be realized using this coarse-grained description.

A model of insulin fibrils derived from the x-ray crystal structure of a monomeric insulin (despentapeptide insulin).

PubMed

Brange, J; Dodson, G G; Edwards, D J; Holden, P H; Whittingham, J L

1997-04-01

The crystal structure of despentapeptide insulin, a monomeric insulin, has been refined at 1.3 A spacing and subsequently used to predict and model the organization in the insulin fibril. The model makes use of the contacts in the densely packed despentapeptide insulin crystal, and takes into account other experimental evidence, including binding studies with Congo red. The dimensions of this model fibril correspond well with those measured experimentally, and the monomer-monomer contacts within the fibril are in accordance with the known physical chemistry of insulin fibrils. Using this model, it may be possible to predict mutations in insulin that might alleviate problems associated with fibril formation during insulin therapy.

A mimic study on effects of fluoride on tooth enamel structures

NASA Astrophysics Data System (ADS)

Ma, Guobin; Wang, Mu; Liu, Xiang Yang

2010-03-01

Tooth enamel is the hardest tissue in human body, and this superior mechanical property is contributed by its unique microstructures, i.e., oriented growth of rod-like apatite crystals into basic structural units called the prisms Fluoride (F^-) has been recognized to have significant effects on the physical and chemical properties of tooth enamel. However, the role of F^- on microstructures of apatite crystals is not well understood yet. Here we report a detailed investigation on the topic. Mimic in vitro growth of tooth enamel structures is performed at the biophysical conditions in simulated body fluids, using belt-like hydroxyapatite crystals as substrates It shows that F^- on the order of 0.1 mM will dramatically change the morphology of the grown crystals from irregular slabs to nano-needles, and the needles are aligned along the substrate with an average misorientation of ˜12 . Branched growth of bundles of nano-needles occurs with further increase of F^-, and finally, growth of highly porous structures as well as microspheres takes place when the F^- concentration exceeds 5 mM. In comparison with real tooth enamel structures, the relationship between enamel microstructures and tooth caries as well as fluorosis is discussed.

Symmetry-lowering lattice distortion at the spin reorientation in MnBi single crystals

DOE PAGES

McGuire, Michael A.; Cao, Huibo; Chakoumakos, Bryan C.; ...

2014-11-18

Here we report structural and physical properties determined by measurements on large single crystals of the anisotropic ferromagnet MnBi. The findings support the importance of magnetoelastic effects in this material. X-ray diffraction reveals a structural phase transition at the spin reorientation temperature T SR = 90 K. The distortion is driven by magneto-elastic coupling, and upon cooling transforms the structure from hexagonal to orthorhombic. Heat capacity measurements show a thermal anomaly at the crystallographic transition, which is suppressed rapidly by applied magnetic fields. Effects on the transport and anisotropic magnetic properties of the single crystals are also presented. Increasing anisotropymore » of the atomic displacement parameters for Bi with increasing temperature above T SR is revealed by neutron diffraction measurements. It is likely that this is directly related to the anisotropic thermal expansion in MnBi, which plays a key role in the spin reorientation and magnetocrystalline anisotropy. Finally, the identification of the true ground state crystal structure reported here may be important for future experimental and theoretical studies of this permanent magnet material, which have to date been performed and interpreted using only the high temperature structure.« less

FDTD and transfer matrix methods for evaluating the performance of photonic crystal based microcavities for exciton-polaritons

NASA Astrophysics Data System (ADS)

Liu, Yi-Cheng; Byrnes, Tim

2016-11-01

We investigate alternative microcavity structures for exciton-polaritons consisting of photonic crystals instead of distributed Bragg reflectors. Finite-difference time-domain simulations and scattering transfer matrix methods are used to evaluate the cavity performance. The results are compared with conventional distributed Bragg reflectors. We find that in terms of the photon lifetime, the photonic crystal based microcavities are competitive, with typical lifetimes in the region of ∼20 ps being achieved. The photonic crystal microcavities have the advantage that they are compact and are frequency adjustable, showing that they are viable to investigate exciton-polariton condensation physics.

A composite hydrogels-based photonic crystal multi-sensor

NASA Astrophysics Data System (ADS)

Chen, Cheng; Zhu, Zhigang; Zhu, Xiangrong; Yu, Wei; Liu, Mingju; Ge, Qiaoqiao; Shih, Wei-Heng

2015-04-01

A facile route to prepare stimuli-sensitive poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) gelated crystalline colloidal array photonic crystal material was developed. PVA was physically gelated by utilizing an ethanol-assisted method, the resulting hydrogel/crystal composite film was then functionalized with PAA to form an interpenetrating hydrogel film. This sensor film is able to efficiently diffract the visible light and rapidly respond to various environmental stimuli such as solvent, pH and strain, and the accompanying structural color shift can be repeatedly changed and easily distinguished by naked eye.

KMCThinFilm: A C++ Framework for the Rapid Development of Lattice Kinetic Monte Carlo (kMC) Simulations of Thin Film Growth

DTIC Science & Technology

2015-09-01

direction, so if the simulation domain is set to be a certain size, then that presents a hard ceiling on the thickness of a film that may be grown in...FFA, Los J, Cuppen HM, Bennema P, Meekes H. MONTY:  Monte Carlo crystal growth on any crystal structure in any crystallographic orientation...mhoffman.github.io/kmos/. 23. Kiravittaya S, Schmidt OG. Quantum-dot crystal defects. Applied Physics Letters. 2008;93:173109. 24. Leetmaa M

Physics of Colloids in Space-2 (PCS-2)

NASA Technical Reports Server (NTRS)

Sankaran, Subramanian; Gasser, Urs; Manley, Suliana; Valentine, Megan; Prasad, Vikram; Rudhardt, Daniel; Bailey, Arthur; Dinsmore, Anthony; Segre, Phil; Doherty, Michael P.

2001-01-01

The Physics of Colloids-2 (PCS-2) experiment is aimed at investigating the basic physical properties of several types of colloidal suspensions. The three broad classes of colloidal systems of interest are binary colloids, colloid-polymer mixtures, and fractal gels. The objective is to understand their phase behavior as well as the kinetics of the phase transitions in the absence of gravity. The nucleation, growth, and morphology characteristics of the crystals and gels that form would be studied using confocal microscopy. These will be observed directly with excellent time resolution, and therefore extensive information about the different phases and their growth mechanisms will be gained. With the laser tweezers, it will be possible to measure the strength of these structures and to modify them in a controlled way, and the spectrophotometer will provide the possibility to probe their optical properties. We believe that this experiment will provide the basis for future 'colloid engineering' in which complicated structures with novel properties (e.g., photonic crystals) will be grown by controlled self-assembly.

The antifriction behaviours of ?

NASA Astrophysics Data System (ADS)

Yan, Feng-yuan; Xue, Qun-ji

1997-03-01

In this paper, the antifriction behaviours of 0022-3727/30/5/010/img2 (3:1) molecules and their crystal powder were evaluated by different methods. It was found that the 0022-3727/30/5/010/img2 crystal powder possessed hexagonal close packed (hcp) crystal structure with a = 10.1 Å and c = 16.55 Å, and a transformation of crystal structure from hcp to face centred cubic (fcc) occurred easily during friction (burnishing). It was confirmed that two kinds of process, breakage of 0022-3727/30/5/010/img2 powder coagulated by nanoscale single crystals and rearrangement of the molecules along the friction direction, had occurred under the friction force. The extreme pressure (EP) performance of 0022-3727/30/5/010/img2 as an additive in paraffin liquid was investigated on an SRV oscillating wear machine. It was found that the extreme pressure load (EP value) of paraffin liquid was increased by dispersion of 0022-3727/30/5/010/img2 powder, accompanied by a slight improvement in the antifriction behaviour. it was confirmed that the improvement in EP value and antifriction behaviour of oil was dependent on the crystal structure of 0022-3727/30/5/010/img2 powder, but independent of the spherical molecular structure of 0022-3727/30/5/010/img8 or 0022-3727/30/5/010/img9. The burnishing experimental results also proved that the antifriction behaviour was determined by the crystal structure and had no relation to the molecular structure. It was also found that fullerenes possessed some physical properties similar to those of graphite. Since the formation of compact fullerenes with high shear strength during friction can be effectively prevented by some other lubricants, it is suggested that fullerenes should be mixed with other lubricants for tribological application.

RH-temperature phase diagrams of hydrate forming deliquescent crystalline ingredients.

PubMed

Allan, Matthew; Mauer, Lisa J

2017-12-01

Several common deliquescent crystalline food ingredients (including glucose and citric acid) are capable of forming crystal hydrate structures. The propensity of such crystals to hydrate/dehydrate or deliquesce is dependent on the environmental temperature and relative humidity (RH). As an anhydrous crystal converts to a crystal hydrate, water molecules internalize into the crystal structure resulting in different physical properties. Deliquescence is a solid-to-solution phase transformation. RH-temperature phase diagrams of the food ingredients alpha-d-glucose and citric acid, along with sodium sulfate, were produced using established and newly developed methods. Each phase diagram included hydrate and anhydrate deliquescence boundaries, the anhydrate-hydrate phase boundary, and the peritectic temperature (above which the hydrate was no longer stable). This is the first report of RH-temperature phase diagrams of glucose and citric acid, information which is beneficial for selecting storage and processing conditions to promote or avoid hydrate formation or loss and/or deliquescence. Copyright © 2017 Elsevier Ltd. All rights reserved.

Machine learning for the structure-energy-property landscapes of molecular crystals.

PubMed

Musil, Félix; De, Sandip; Yang, Jack; Campbell, Joshua E; Day, Graeme M; Ceriotti, Michele

2018-02-07

Molecular crystals play an important role in several fields of science and technology. They frequently crystallize in different polymorphs with substantially different physical properties. To help guide the synthesis of candidate materials, atomic-scale modelling can be used to enumerate the stable polymorphs and to predict their properties, as well as to propose heuristic rules to rationalize the correlations between crystal structure and materials properties. Here we show how a recently-developed machine-learning (ML) framework can be used to achieve inexpensive and accurate predictions of the stability and properties of polymorphs, and a data-driven classification that is less biased and more flexible than typical heuristic rules. We discuss, as examples, the lattice energy and property landscapes of pentacene and two azapentacene isomers that are of interest as organic semiconductor materials. We show that we can estimate force field or DFT lattice energies with sub-kJ mol -1 accuracy, using only a few hundred reference configurations, and reduce by a factor of ten the computational effort needed to predict charge mobility in the crystal structures. The automatic structural classification of the polymorphs reveals a more detailed picture of molecular packing than that provided by conventional heuristics, and helps disentangle the role of hydrogen bonded and π-stacking interactions in determining molecular self-assembly. This observation demonstrates that ML is not just a black-box scheme to interpolate between reference calculations, but can also be used as a tool to gain intuitive insights into structure-property relations in molecular crystal engineering.

Rapid and reversible photoinduced switching of a rotaxane crystal

NASA Astrophysics Data System (ADS)

Chen, Kai-Jen; Tsai, Ya-Ching; Suzaki, Yuji; Osakada, Kohtaro; Miura, Atsushi; Horie, Masaki

2016-11-01

Crystalline phase transitions caused by external stimuli have been used to detect physical changes in the solid-state properties. This study presents the mechanical switching of crystals of ferrocene-containing rotaxane controlled by focused laser light. The expansion and contraction of the crystals can be driven by turning on and off laser light at 445 nm. The irradiation-induced expansion of the crystal involves elongation along the a, b and c axes at 30 °C, whereas heating of the crystal at 105 °C causes the shortening of c axis. The expansions reversibly occur and have the advantage of a rapid relaxation (reverse) process. Single-crystal X-ray crystallography reveals the detailed structural changes of the molecules, corresponding to a change in the size of the crystals on laser irradiation. This molecular crystal behaviour induced by laser irradiation, is demonstrated for the remote control of objects, namely, microparticle transport and microswitching in an electric circuit.

Control of the conformations of ion Coulomb crystals in a Penning trap

PubMed Central

Mavadia, Sandeep; Goodwin, Joseph F.; Stutter, Graham; Bharadia, Shailen; Crick, Daniel R.; Segal, Daniel M.; Thompson, Richard C.

2013-01-01

Laser-cooled atomic ions form ordered structures in radiofrequency ion traps and in Penning traps. Here we demonstrate in a Penning trap the creation and manipulation of a wide variety of ion Coulomb crystals formed from small numbers of ions. The configuration can be changed from a linear string, through intermediate geometries, to a planar structure. The transition from a linear string to a zigzag geometry is observed for the first time in a Penning trap. The conformations of the crystals are set by the applied trap potential and the laser parameters, and agree with simulations. These simulations indicate that the rotation frequency of a small crystal is mainly determined by the laser parameters, independent of the number of ions and the axial confinement strength. This system has potential applications for quantum simulation, quantum information processing and tests of fundamental physics models from quantum field theory to cosmology. PMID:24096901

Simulation and understanding of atomic and molecular quantum crystals

NASA Astrophysics Data System (ADS)

Cazorla, Claudio; Boronat, Jordi

2017-07-01

Quantum crystals abound in the whole range of solid-state species. Below a certain threshold temperature the physical behavior of rare gases (He 4 and Ne), molecular solids (H2 and CH4 ), and some ionic (LiH), covalent (graphite), and metallic (Li) crystals can be explained only in terms of quantum nuclear effects (QNE). A detailed comprehension of the nature of quantum solids is critical for achieving progress in a number of fundamental and applied scientific fields such as planetary sciences, hydrogen storage, nuclear energy, quantum computing, and nanoelectronics. This review describes the current physical understanding of quantum crystals formed by atoms and small molecules, as well as the wide palette of simulation techniques that are used to investigate them. Relevant aspects in these materials such as phase transformations, structural properties, elasticity, crystalline defects, and the effects of reduced dimensionality are discussed thoroughly. An introduction to quantum Monte Carlo techniques, which in the present context are the simulation methods of choice, and other quantum simulation approaches (e.g., path-integral molecular dynamics and quantum thermal baths) is provided. The overarching objective of this article is twofold: first, to clarify in which crystals and physical situations the disregard of QNE may incur in important bias and erroneous interpretations. And second, to promote the study and appreciation of QNE, a topic that traditionally has been treated in the context of condensed matter physics, within the broad and interdisciplinary areas of materials science.

Nonlinear coherent structures in granular crystals

NASA Astrophysics Data System (ADS)

Chong, C.; Porter, Mason A.; Kevrekidis, P. G.; Daraio, C.

2017-10-01

The study of granular crystals, which are nonlinear metamaterials that consist of closely packed arrays of particles that interact elastically, is a vibrant area of research that combines ideas from disciplines such as materials science, nonlinear dynamics, and condensed-matter physics. Granular crystals exploit geometrical nonlinearities in their constitutive microstructure to produce properties (such as tunability and energy localization) that are not conventional to engineering materials and linear devices. In this topical review, we focus on recent experimental, computational, and theoretical results on nonlinear coherent structures in granular crystals. Such structures—which include traveling solitary waves, dispersive shock waves, and discrete breathers—have fascinating dynamics, including a diversity of both transient features and robust, long-lived patterns that emerge from broad classes of initial data. In our review, we primarily discuss phenomena in one-dimensional crystals, as most research to date has focused on such scenarios, but we also present some extensions to two-dimensional settings. Throughout the review, we highlight open problems and discuss a variety of potential engineering applications that arise from the rich dynamic response of granular crystals.

Dissertation Award in Nuclear Physics Recipient: Astromaterials in Neutron Stars

NASA Astrophysics Data System (ADS)

Caplan, Matthew E.

2017-09-01

Stars freeze. As they age and cool white dwarfs and neutron stars crystallize, with remarkable materials forming in their interiors. These `astromaterials' have structures similar to terrestrial crystalline solids and liquid crystals, though they are over a trillion times denser. Notably, because their material properties affect the observable properties of the star, astromaterials must be understood to interpret observations of neutron stars. Thus, astromaterial science can be thought of as an interdisciplinary field, using techniques from material science to study nuclear physics systems with astrophysical relevance. In this talk, I will discuss recent results from simulations of astromaterials and how we use these results to interpret observations of neutron stars in X-ray binaries. In addition, I will discuss how nuclear pasta, in neutron stars, forms structures remarkably similar to biophysical membranes seen in living organisms.

Glass-based confined structures enabling light control

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chiappini, Andrea; Normani, Simone; Chiasera, Alessandro

2015-04-24

When a luminescent ion is confined in a system characterized by one or more specific properties such as spatial size, geometrical dimension and shape, refractive index, local crystal field, cut-off vibrational energy and so on, it's possible to control its emission. The control of branching ratios as a function of the composition, the luminescence enhancement induced by a photonic crystal, or the laser action in a microresonator, are well known examples of light control. Photonic glass-based structures are extremely viable systems to exploit the above mentioned properties and in our research team we have successfully fabricated luminescent photonic structures bymore » different techniques, including sol-gel, rf sputtering, drawing, melting, and physical vapour deposition. Here we will discuss some of them with the aim to make the reader aware of the chemical-physical properties related to each specific system. We will demonstrate that glass ceramic waveguides in some cases present superior spectroscopic properties in respect to the parent glass, that compositional properties can play a positive role in reducing luminescence quenching and in developing novel planar waveguides and fibers, that colloids allow to obtain high internal quantum efficiency and that photonic crystals, microcavities and microresonators can enable the handling of the rare earth luminescence. Finally, the pros and cons of the systems and of the different techniques employed for their fabrication will be discussed and some perspectives concerning the glass photonics will be proposed looking at both possible applications and investigation of physical properties.« less

Novel growth techniques of group-IV based semiconductors on insulator for next-generation electronics

NASA Astrophysics Data System (ADS)

Miyao, Masanobu; Sadoh, Taizoh

2017-05-01

Recent progress in the crystal growth of group-IV-based semiconductor-on-insulators is reviewed from physical and technological viewpoints. Liquid-phase growth based on SiGe-mixing-triggered rapid-melting growth enables formation of hybrid (100) (110) (111)-orientation Ge-on-insulator (GOI) structures, which show defect-free GOI with very high carrier mobility (˜1040 cm2 V-1 s-1). Additionally, SiGe mixed-crystals with laterally uniform composition were obtained by eliminating segregation phenomena during the melt-back process. Low-temperature solid-phase growth has been explored by combining this process with ion-beam irradiation, additional doping of group-IV elements, metal induced lateral crystallization with/without electric field, and metal-induced layer exchange crystallization. These efforts have enabled crystal growth on insulators below 400 °C, achieving high carrier mobility (160-320 cm2 V-1 s-1). Moreover, orientation-controlled SiGe and Ge films on insulators have been obtained below the softening temperatures of conventional plastic films (˜300 °C). Detailed characterization provides an understanding of physical phenomena behind these crystal growth techniques. Applying these methods when fabricating next-generation electronics is also discussed.

Impact of Protein-Metal Ion Interactions on the Crystallization of Silk Fibroin Protein

NASA Astrophysics Data System (ADS)

Hu, Xiao; Lu, Qiang; Kaplan, David; Cebe, Peggy

2009-03-01

Proteins can easily form bonds with a variety of metal ions, which provides many unique biological functions for the protein structures, and therefore controls the overall structural transformation of proteins. We use advanced thermal analysis methods such as temperature modulated differential scanning calorimetry and quasi-isothermal TMDSC, combined with Fourier transform infrared spectroscopy, and scanning electron microscopy, to investigate the protein-metallic ion interactions in Bombyx mori silk fibroin proteins. Silk samples were mixed with different metal ions (Ca^2+, K^+, Ma^2+, Na^+, Cu^2+, Mn^2+) with different mass ratios, and compared with the physical conditions in the silkworm gland. Results show that all metallic ions can directly affect the crystallization behavior and glass transition of silk fibroin. However, different ions tend to have different structural impact, including their role as plasticizer or anti-plasticizer. Detailed studies reveal important information allowing us better to understand the natural silk spinning and crystallization process.

Faceting, composition and crystal phase evolution in III-V antimonide nanowire heterostructures revealed by combining microscopy techniques.

PubMed

Xu, Tao; Dick, Kimberly A; Plissard, Sébastien; Nguyen, Thanh Hai; Makoudi, Younes; Berthe, Maxime; Nys, Jean-Philippe; Wallart, Xavier; Grandidier, Bruno; Caroff, Philippe

2012-03-09

III-V antimonide nanowires are among the most interesting semiconductors for transport physics, nanoelectronics and long-wavelength optoelectronic devices due to their optimal material properties. In order to investigate their complex crystal structure evolution, faceting and composition, we report a combined scanning electron microscopy (SEM), transmission electron microscopy (TEM), and scanning tunneling microscopy (STM) study of gold-nucleated ternary InAs/InAs(1-x)Sb(x) nanowire heterostructures grown by molecular beam epitaxy. SEM showed the general morphology and faceting, TEM revealed the internal crystal structure and ternary compositions, while STM was successfully applied to characterize the oxide-free nanowire sidewalls, in terms of nanofaceting morphology, atomic structure and surface composition. The complementary use of these techniques allows for correlation of the morphological and structural properties of the nanowires with the amount of Sb incorporated during growth. The addition of even a minute amount of Sb to InAs changes the crystal structure from perfect wurtzite to perfect zinc blende, via intermediate stacking fault and pseudo-periodic twinning regimes. Moreover, the addition of Sb during the axial growth of InAs/InAs(1-x)Sb(x) heterostructure nanowires causes a significant conformal lateral overgrowth on both segments, leading to the spontaneous formation of a core-shell structure, with an Sb-rich shell.

Observation of steric hindrance effect controlling crystal packing structures and physical properties in three new isomeric nitronyl nitroxide radicals

NASA Astrophysics Data System (ADS)

Zhao, Hai-Rong; Sun, Jia-Sen; Sui, Yun-Xia; Ren, Xiao-Ming; Yao, Bin-Qian; Shen, Lin-Jiang; Meng, Qing-Jin

2009-07-01

Three isomeric nitronyl nitroxide radical compounds, 2-[ n-( N-benzyl)pyridinium]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide bromide ( n = 2, 3 and 4 for 1, 2 and 3, respectively), have been synthesized and structurally characterized. The influence of steric hindrance on the molecular packing structures and physical properties has been observed. In the radical 1, such steric hindrance leads to a folding conformation of the imidazoline and benzene rings and the intramolecular C-H…π interaction between the methyl group and the benzene ring. There is no such effect in 2 and 3. In crystal of 2, there are the intermolecular C-H…π between methyl groups and benzene ring and intermolecular π…π stacking interaction between pyridine and benzene rings. Crystal of 2 with a chiral space group P2 12 12 1 shows the SHG response about 0.4 times as that of urea. In crystal of 3, there are three symmetry-independent radical molecules, which form an unusually six-membered supramolecular ring via intermolecular O…π interactions. For the solid sample of 3, the X-band EPR exhibits an axially symmetric signal and magnetic susceptibility data suggest intermolecular antiferromagnetic (AFM) coupling interactions and very weak intermolecular ferromagnetic (FM) coupling interactions which is more likely caused by magnetic anisotropy, while measurements of both 1 and 2 show isotropic X-band EPR signals and simple Currie-Weiss magnetic behavior.

Precision Crystal Calorimeters in High Energy Physics

ScienceCinema

Ren-Yuan Zhu

2017-12-09

Precision crystal calorimeters traditionally play an important role in high energy physics experiments. In the last two decades, it faces a challenge to maintain its precision in a hostile radiation environment. This paper reviews the performance of crystal calorimeters constructed for high energy physics experiments and the progress achieved in understanding crystal’s radiation damage as well as in developing high quality scintillating crystals for particle physics. Potential applications of new generation scintillating crystals of high density and high light yield, such as LSO and LYSO, in particle physics experiments is also discussed.

Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts.

PubMed

Liang, Miao; Wang, Libing; Liu, Xia; Qi, Wei; Su, Rongxin; Huang, Renliang; Yu, Yanjun; He, Zhimin

2013-06-21

Bio-nanomaterials fabricated using a bioinspired templating technique represent a novel class of composite materials with diverse applications in biomedical, electronic devices, drug delivery, and catalysis. In this study, Au nanoparticles (NPs) are synthesized within the solvent channels of cross-linked lysozyme crystals (CLLCs) in situ without the introduction of extra chemical reagents or physical treatments. The as-prepared AuNPs-in-protein crystal hybrid materials are characterized by light microscopy, transmission electron microscopy, x-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Small AuNPs with narrow size distribution reveal the restriction effects of the porous structure in the lysozyme crystals. These composite materials are proven to be active heterogeneous catalysts for the reduction of 4-nitrophenol to 4-aminophenol. These catalysts can be easily recovered and reused at least 20 times because of the physical stability and macro-dimension of CLLCs. This work is the first to use CLLCs as a solid biotemplate for the preparation of recyclable high-performance catalysts.

Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts

NASA Astrophysics Data System (ADS)

Liang, Miao; Wang, Libing; Liu, Xia; Qi, Wei; Su, Rongxin; Huang, Renliang; Yu, Yanjun; He, Zhimin

2013-06-01

Bio-nanomaterials fabricated using a bioinspired templating technique represent a novel class of composite materials with diverse applications in biomedical, electronic devices, drug delivery, and catalysis. In this study, Au nanoparticles (NPs) are synthesized within the solvent channels of cross-linked lysozyme crystals (CLLCs) in situ without the introduction of extra chemical reagents or physical treatments. The as-prepared AuNPs-in-protein crystal hybrid materials are characterized by light microscopy, transmission electron microscopy, x-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Small AuNPs with narrow size distribution reveal the restriction effects of the porous structure in the lysozyme crystals. These composite materials are proven to be active heterogeneous catalysts for the reduction of 4-nitrophenol to 4-aminophenol. These catalysts can be easily recovered and reused at least 20 times because of the physical stability and macro-dimension of CLLCs. This work is the first to use CLLCs as a solid biotemplate for the preparation of recyclable high-performance catalysts.

Diode-pumped laser performance of Tm:Sc2SiO5 crystal at 1971 nm

NASA Astrophysics Data System (ADS)

Liu, Bin; Zheng, Li-He; Wang, Qing-Guo; Liu, Jun-Fang; Su, Liang-Bi; Tang, Hui-Li; Liu, Jie; Fan, Xiu-Wei; Wu, Feng; Luo, Ping; Zhao, Heng-Yu; Shi, Jiao-Jiao; He, Nuo-Tian; Li, Na; Li, Qiu; Guo, Chao; Xu, Xiao-Dong; Wang, Zhan-Shan; Xu, Jun

2017-08-01

Not Available Project supported by the Shanghai Municipal Engineering Research Center for Sapphire Crystals, China (Grant No. 14DZ2252500), the Fund of Key Laboratory of Optoelectronic Materials Chemistry and Physics, Chinese Academy of Sciences (Grant No. 2008DP17301), the Fundamental Research Funds for the Central Universities, the National Natural Science Foundation of China and the China Academy of Engineering Physics Joint Fund (Grant No. U1530152), the National Natural Science Foundation of China (Grant Nos. 61475177 and 61621001), the Shanghai Municipal Natural Science Foundation, China (Grant No. 13ZR1446100), and the MDE Key Laboratory of Advanced Micro-Structured Materials.

Effect of high pressure microfluidization on the crystallization behavior of palm stearin - palm olein blends.

PubMed

Han, Lijuan; Li, Lin; Li, Bing; Zhao, Lei; Liu, Guoqin; Liu, Xinqi; Wang, Xuede

2014-04-24

Moderate and high microfluidization pressures (60 and 120 MPa) and different treatment times (once and twice) were used to investigate the effect of high-pressure microfluidization (HPM) treatment on the crystallization behavior and physical properties of binary mixtures of palm stearin (PS) and palm olein (PO). The polarized light microscopy (PLM), texture analyzer, X-ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques were applied to analyze the changes in crystal network structure, hardness, polymorphism and thermal property of the control and treated blends. PLM results showed that HPM caused significant reductions in maximum crystal diameter in all treated blends, and thus led to changes in the crystal network structure, and finally caused higher hardness in than the control blends. The XRD study demonstrated that HPM altered crystalline polymorphism. The HPM-treated blends showed a predominance of the more stable β' form, which is of more interest for food applications, while the control blend had more α- and β-form. This result was further confirmed by DSC observations. These changes in crystallization behavior indicated that HPM treatment was more likely to modify the crystallization processes and nucleation mechanisms.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramadhar, Timothy R.; Zheng, Shao-Liang; Chen, Yu-Sheng

This report describes complete practical guidelines and insights for the crystalline sponge method, which have been derived through the first use of synchrotron radiation on these systems, and includes a procedure for faster synthesis of the sponges. These guidelines will be applicable to crystal sponge data collected at synchrotrons or in-house facilities, and will allow researchers to obtain reliable high-quality data and construct chemically and physically sensible models for guest structural determination. A detailed set of synthetic and crystallographic guidelines for the crystalline sponge method based upon the analysis of expediently synthesized crystal sponges using third-generation synchrotron radiation are reported.more » The procedure for the synthesis of the zinc-based metal–organic framework used in initial crystal sponge reports has been modified to yield competent crystals in 3 days instead of 2 weeks. These crystal sponges were tested on some small molecules, with two being unexpectedly difficult cases for analysis with in-house diffractometers in regard to data quality and proper space-group determination. These issues were easily resolved by the use of synchrotron radiation using data-collection times of less than an hour. One of these guests induced a single-crystal-to-single-crystal transformation to create a larger unit cell with over 500 non-H atoms in the asymmetric unit. This led to a non-trivial refinement scenario that afforded the best Flack x absolute stereochemical determination parameter to date for these systems. The structures did not require the use of PLATON/SQUEEZE or other solvent-masking programs, and are the highest-quality crystalline sponge systems reported to date where the results are strongly supported by the data. A set of guidelines for the entire crystallographic process were developed through these studies. In particular, the refinement guidelines include strategies to refine the host framework, locate guests and determine occupancies, discussion of the proper use of geometric and anisotropic displacement parameter restraints and constraints, and whether to perform solvent squeezing/masking. The single-crystal-to-single-crystal transformation process for the crystal sponges is also discussed. The presented general guidelines will be invaluable for researchers interested in using the crystalline sponge method at in-house diffraction or synchrotron facilities, will facilitate the collection and analysis of reliable high-quality data, and will allow construction of chemically and physically sensible models for guest structural determination.« less

On the Chemistry and Physical Properties of Flux and Floating Zone Grown SmB6 Single Crystals

PubMed Central

Phelan, W. A.; Koohpayeh, S. M.; Cottingham, P.; Tutmaher, J. A.; Leiner, J. C.; Lumsden, M. D.; Lavelle, C. M.; Wang, X. P.; Hoffmann, C.; Siegler, M. A.; Haldolaarachchige, N.; Young, D. P.; McQueen, T. M.

2016-01-01

Recent theoretical and experimental findings suggest the long-known but not well understood low temperature resistance plateau of SmB6 may originate from protected surface states arising from a topologically non-trivial bulk band structure having strong Kondo hybridization. Yet others have ascribed this feature to impurities, vacancies, and surface reconstructions. Given the typical methods used to prepare SmB6 single crystals, flux and floating-zone procedures, such ascriptions should not be taken lightly. We demonstrate how compositional variations and/or observable amounts of impurities in SmB6 crystals grown using both procedures affect the physical properties. From X-ray diffraction, neutron diffraction, and X-ray computed tomography experiments we observe that natural isotope containing (SmB6) and doubly isotope enriched (154Sm11B6) crystals prepared using aluminum flux contain co-crystallized, epitaxial aluminum. Further, a large, nearly stoichiometric crystal of SmB6 was successfully grown using the float-zone technique; upon continuing the zone melting, samarium vacancies were introduced. These samarium vacancies drastically alter the resistance and plateauing magnitude of the low temperature resistance compared to stoichiometric SmB6. These results highlight that impurities and compositional variations, even at low concentrations, must be considered when collecting/analyzing physical property data of SmB6. Finally, a more accurate samarium-154 coherent neutron scattering length, 8.9(1) fm, is reported. PMID:26892648

On the Chemistry and Physical Properties of Flux and Floating Zone Grown SmB 6 Single Crystals

DOE PAGES

Phelan, W. A.; Koohpayeh, S. M.; Cottingham, P.; ...

2016-02-19

Recent theoretical and experimental findings suggest the long-known but not well understood low temperature resistance plateau of SmB 6 may originate from protected surface states arising from a topologically non-trivial bulk band structure having strong Kondo hybridization. Yet others have ascribed this feature to impurities, vacancies, and surface reconstructions. Given the typical methods used to prepare SmB 6 single crystals, flux and floating-zone procedures, such ascriptions should not be taken lightly. We demonstrate how compositional variations and/or observable amounts of impurities in SmB 6 crystals grown using both procedures affect the physical properties. From X-ray diffraction, neutron diffraction, and X-raymore » computed tomography experiments we observe that natural isotope containing (SmB 6) and doubly isotope enriched ( 154Sm 11B 6) crystals prepared using aluminum flux contain co-crystallized, epitaxial aluminum. Further, a large, nearly stoichiometric crystal of SmB 6 was successfully grown using the float-zone technique; upon continuing the zone melting, samarium vacancies were introduced. These samarium vacancies drastically alter the resistance and plateauing magnitude of the low temperature resistance compared to stoichiometric SmB 6. Finally, these results highlight that impurities and compositional variations, even at low concentrations, must be considered when collecting/analyzing physical property data of SmB 6. Finally, a more accurate samarium-154 coherent neutron scattering length, 8.9(1) fm, is reported.« less

Interatomic Potentials for Structure Simulation of Alkaline-Earth Cuprates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eremin, N.N.; Leonyuk, L.I.; Urusov, V.S.

2001-05-01

A specific potential model of interionic interactions was derived in which the crystal structures of alkaline-earth cuprates were satisfactorily described and some of their physical properties were predicted. It was found that a harmonic three-particle O-Cu-O potential and some Morse-type contributions to the simple Buckingham-type Cu-O repulsive potential enable one to improve essentially the results of crystal structure modeling for cuprates. The obtained potential set seems to be well transferable for different cuprates, despite the variety in linkages of the CuO{sub 4} groups. In the present work this potential set model was applied in the crystal structure modeling for Ca{submore » 2}CuO{sub 3}, CaCuO{sub 2}, SrCuO{sub 3}, (Sr{sub 1.19}Ca{sub 0.73})Cu{sub 2}O{sub 4}, and BaCuO{sub 2}. Some elastic and energetic properties of the compounds under question were predicted.« less

Effect of potassium doping on electronic structure and thermoelectric properties of topological crystalline insulator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roychowdhury, Subhajit; Biswas, Kanishka, E-mail: kanishka@jncasr.ac.in; Sandhya Shenoy, U.

2016-05-09

Topological crystalline insulator (TCI), Pb{sub 0.6}Sn{sub 0.4}Te, exhibits metallic surface states protected by crystal mirror symmetry with negligibly small band gap. Enhancement of its thermoelectric performances needs tuning of its electronic structure particularly through engineering of its band gap. While physical perturbations tune the electronic structure of TCI by breaking of the crystal mirror symmetry, chemical means such as doping have been more attractive recently as they result in better thermoelectric performance in TCIs. Here, we demonstrate that K doping in TCI, Pb{sub 0.6}Sn{sub 0.4}Te, breaks the crystal mirror symmetry locally and widens electronic band gap, which is confirmed bymore » direct electronic absorption spectroscopy and electronic structure calculations. K doping in Pb{sub 0.6}Sn{sub 0.4}Te increases p-type carrier concentration and suppresses the bipolar conduction via widening a band gap, which collectively boosts the thermoelectric figure of merit (ZT) to 1 at 708 K.« less

Manipulation of photons at the surface of three-dimensional photonic crystals.

PubMed

Ishizaki, Kenji; Noda, Susumu

2009-07-16

In three-dimensional (3D) photonic crystals, refractive-index variations with a periodicity comparable to the wavelength of the light passing through the crystal give rise to so-called photonic bandgaps, which are analogous to electronic bandgaps for electrons moving in the periodic electrostatic potential of a material's crystal structure. Such 3D photonic bandgap crystals are envisioned to become fundamental building blocks for the control and manipulation of photons in optical circuits. So far, such schemes have been pursued by embedding artificial defects and light emitters inside the crystals, making use of 3D bandgap directional effects. Here we show experimentally that photons can be controlled and manipulated even at the 'surface' of 3D photonic crystals, where 3D periodicity is terminated, establishing a new and versatile route for photon manipulation. By making use of an evanescent-mode coupling technique, we demonstrate that 3D photonic crystals possess two-dimensional surface states, and we map their band structure. We show that photons can be confined and propagate through these two-dimensional surface states, and we realize their localization at arbitrary surface points by designing artificial surface-defect structures through the formation of a surface-mode gap. Surprisingly, the quality factors of the surface-defect mode are the largest reported for 3D photonic crystal nanocavities (Q up to approximately 9,000). In addition to providing a new approach for photon manipulation by photonic crystals, our findings are relevant for the generation and control of plasmon-polaritons in metals and the related surface photon physics. The absorption-free nature of the 3D photonic crystal surface may enable new sensing applications and provide routes for the realization of efficient light-matter interactions.

Effect of H{sup +} implantation on the optical properties of semi-insulating GaAs crystals in the IR spectral region

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klyui, N. I.; Lozinskii, V. B., E-mail: lvb@isp.kiev.ua; Liptuga, A. I.

2017-03-15

The optical properties of semi-insulating GaAs crystals subjected to multienergy hydrogen-ion implantation and treatment in a high-frequency electromagnetic field are studied in the infrared spectral region. It is established that such combined treatment provides a means for substantially increasing the transmittance of GaAs crystals to values characteristic of crystals of high optical quality. On the basis of analysis of the infrared transmittance and reflectance data, Raman spectroscopy data, and atomic-force microscopy data on the surface morphology of the crystals, a physical model is proposed to interpret the effects experimentally observed in the crystals. The model takes into account the interactionmore » of radiation defects with the initial structural defects in the crystals as well as the effect of compensation of defect centers by hydrogen during high-frequency treatment.« less

Advanced Methods of Protein Crystallization.

PubMed

Moreno, Abel

2017-01-01

This chapter provides a review of different advanced methods that help to increase the success rate of a crystallization project, by producing larger and higher quality single crystals for determination of macromolecular structures by crystallographic methods. For this purpose, the chapter is divided into three parts. The first part deals with the fundamentals for understanding the crystallization process through different strategies based on physical and chemical approaches. The second part presents new approaches involved in more sophisticated methods not only for growing protein crystals but also for controlling the size and orientation of crystals through utilization of electromagnetic fields and other advanced techniques. The last section deals with three different aspects: the importance of microgravity, the use of ligands to stabilize proteins, and the use of microfluidics to obtain protein crystals. All these advanced methods will allow the readers to obtain suitable crystalline samples for high-resolution X-ray and neutron crystallography.

REVIEW: Optics of globular photonic crystals

NASA Astrophysics Data System (ADS)

Gorelik, V. S.

2007-05-01

The results of experimental and theoretical studies of the optical properties of globular photonic crystals - new physical objects having a crystal structure with the lattice period exceeding considerably the atomic size, are presented. As globular photonic crystals, artificial opal matrices consisting of close-packed silica globules of diameter ~200 nm were used. The reflection spectra of these objects characterising the parameters of photonic bands existing in these crystals in the visible spectral region are presented. The idealised models of the energy band structure of photonic crystals investigated in the review give analytic dispersion dependences for the group velocity and the effective photon mass in a globular photonic crystal. The characteristics of secondary emission excited in globular photonic crystals by monochromatic and broadband radiation are presented. The results of investigations of single-photon-excited delayed scattering of light observed in globular photonic crystals exposed to cw UV radiation and radiation from a repetitively pulsed copper vapour laser are presented. The possibilities of using globular photonic crystals as active media for lasing in different spectral regions are considered. It is proposed to use globular photonic crystals as sensitive sensors in optoelectronic devices for molecular analysis of organic and inorganic materials by the modern methods of laser spectroscopy. The results of experimental studies of spontaneous and stimulated globular scattering of light are discussed. The conditions for observing resonance and two-photon-excited delayed scattering of light are found. The possibility of accumulation and localisation of the laser radiation energy inside a globular photonic crystal is reported.

Growing Larger Crystals for Neutron Diffraction

NASA Technical Reports Server (NTRS)

Pusey, Marc

2003-01-01

Obtaining crystals of suitable size and high quality has been a major bottleneck in macromolecular crystallography. With the advent of advanced X-ray sources and methods the question of size has rapidly dwindled, almost to the point where if one can see the crystal then it was big enough. Quality is another issue, and major national and commercial efforts were established to take advantage of the microgravity environment in an effort to obtain higher quality crystals. Studies of the macromolecule crystallization process were carried out in many labs in an effort to understand what affected the resultant crystal quality on Earth, and how microgravity improved the process. While technological improvements are resulting in a diminishing of the minimum crystal size required, neutron diffraction structural studies still require considerably larger crystals, by several orders of magnitude, than X-ray studies. From a crystal growth physics perspective there is no reason why these 'large' crystals cannot be obtained: the question is generally more one of supply than limitations mechanism. This talk will discuss our laboratory s current model for macromolecule crystal growth, with highlights pertaining to the growth of crystals suitable for neutron diffraction studies.

Fluid Physics

NASA Image and Video Library

2003-05-10

These images, from David Weitz’s liquid crystal research, show ordered uniform sized droplets (upper left) before they are dried from their solution. After the droplets are dried (upper right), they are viewed with crossed polarizers that show the deformation caused by drying, a process that orients the bipolar structure of the liquid crystal within the droplets. When an electric field is applied to the dried droplets (lower left), and then increased (lower right), the liquid crystal within the droplets switches its alignment, thereby reducing the amount of light that can be scattered by the droplets when a beam is shone through them.

Electronic and crystal structure of NiTi martensite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanati, M.; Albers, R.C.; Pinski, F.J.

1998-11-01

All of the first-principles electronic-structure calculations for the martensitic structure of NiTi have used the experimental atomic parameters reported by Michal and Sinclair [Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. {bold B37}, 1803 (1981)]. We have used first-principles, full-potential, linear muffin-tin orbital calculations to examine the total energy of all the experimental martensitic structures reported in the literature. We find that another crystal structure, that of Kudoh {ital et al.} [Acta Metall. Mater. {bold 33}, 2049 (1985)], has the lowest total energy at zero temperature. Ground-state and formation energies were calculated for all of the experimental structures. Total andmore » local densities of states were calculated and compared with each other for the structures of both Kudoh {ital et al.} and Michal and Sinclair thinsp {copyright} {ital 1998} {ital The American Physical Society}« less

Crystal growth, physical properties and computational insights of semi-organic non-linear optical crystal diphenylguanidinium perchlorate grown by conventional solvent evaporation method

NASA Astrophysics Data System (ADS)

Kajamuhideen, M. S.; Sethuraman, K.; Ramamurthi, K.; Ramasamy, P.

2018-02-01

A splendid nonlinear optical single crystals diphenylguanidinium perchlorate (DPGP) was lucratively grown by low cost solvent evaporation method with the dimensions of 8 × 4 × 2 mm3. Structural and morphological studies of grown crystal were confirmed using X-ray diffraction studies. The presence of diverse functional groups was identified using FTIR and RAMAN studies. The molecular structure of a grown crystal was inveterate by NMR studies. The optical transmittance of DPGP crystal was analyzed using UV-vis-NIR studies. Photoluminescence spectrum shows sharp, well defined emission peak at 388 nm. Thermal studies assign that adduct is stable with the melting point of 164 °C. Microhardness studies declare that DPGP crystal belongs to the soft material class and their yield strength and elastic stiffness constant values were evaluated. Photoconductivity studies revealed the negative photoconductive nature of DPGP crystal. Second harmonic generation (SHG) efficiency of the DPGP crystal was 1.4 times that of potassium dihydrogen phosphate. Etching studies were carried out for different etching time. The dielectric studies were performed at different frequency. Laser damage threshold properties of DPGP crystal were examined using Nd:YAG laser system. The HOMO-LUMO energy gap evident the charge transfer interaction of the molecule. The calculated first order hyperpolarizability value is 5 times greater than that of urea. Thus, the grown DPGP single crystals are well suited for NLO device fabrications.

Random close packing in protein cores

NASA Astrophysics Data System (ADS)

Gaines, Jennifer C.; Smith, W. Wendell; Regan, Lynne; O'Hern, Corey S.

2016-03-01

Shortly after the determination of the first protein x-ray crystal structures, researchers analyzed their cores and reported packing fractions ϕ ≈0.75 , a value that is similar to close packing of equal-sized spheres. A limitation of these analyses was the use of extended atom models, rather than the more physically accurate explicit hydrogen model. The validity of the explicit hydrogen model was proved in our previous studies by its ability to predict the side chain dihedral angle distributions observed in proteins. In contrast, the extended atom model is not able to recapitulate the side chain dihedral angle distributions, and gives rise to large atomic clashes at side chain dihedral angle combinations that are highly probable in protein crystal structures. Here, we employ the explicit hydrogen model to calculate the packing fraction of the cores of over 200 high-resolution protein structures. We find that these protein cores have ϕ ≈0.56 , which is similar to results obtained from simulations of random packings of individual amino acids. This result provides a deeper understanding of the physical basis of protein structure that will enable predictions of the effects of amino acid mutations to protein cores and interfaces of known structure.

Random close packing in protein cores.

PubMed

Gaines, Jennifer C; Smith, W Wendell; Regan, Lynne; O'Hern, Corey S

2016-03-01

Shortly after the determination of the first protein x-ray crystal structures, researchers analyzed their cores and reported packing fractions ϕ ≈ 0.75, a value that is similar to close packing of equal-sized spheres. A limitation of these analyses was the use of extended atom models, rather than the more physically accurate explicit hydrogen model. The validity of the explicit hydrogen model was proved in our previous studies by its ability to predict the side chain dihedral angle distributions observed in proteins. In contrast, the extended atom model is not able to recapitulate the side chain dihedral angle distributions, and gives rise to large atomic clashes at side chain dihedral angle combinations that are highly probable in protein crystal structures. Here, we employ the explicit hydrogen model to calculate the packing fraction of the cores of over 200 high-resolution protein structures. We find that these protein cores have ϕ ≈ 0.56, which is similar to results obtained from simulations of random packings of individual amino acids. This result provides a deeper understanding of the physical basis of protein structure that will enable predictions of the effects of amino acid mutations to protein cores and interfaces of known structure.

Optimization of crystallization conditions for biological macromolecules.

PubMed

McPherson, Alexander; Cudney, Bob

2014-11-01

For the successful X-ray structure determination of macromolecules, it is first necessary to identify, usually by matrix screening, conditions that yield some sort of crystals. Initial crystals are frequently microcrystals or clusters, and often have unfavorable morphologies or yield poor diffraction intensities. It is therefore generally necessary to improve upon these initial conditions in order to obtain better crystals of sufficient quality for X-ray data collection. Even when the initial samples are suitable, often marginally, refinement of conditions is recommended in order to obtain the highest quality crystals that can be grown. The quality of an X-ray structure determination is directly correlated with the size and the perfection of the crystalline samples; thus, refinement of conditions should always be a primary component of crystal growth. The improvement process is referred to as optimization, and it entails sequential, incremental changes in the chemical parameters that influence crystallization, such as pH, ionic strength and precipitant concentration, as well as physical parameters such as temperature, sample volume and overall methodology. It also includes the application of some unique procedures and approaches, and the addition of novel components such as detergents, ligands or other small molecules that may enhance nucleation or crystal development. Here, an attempt is made to provide guidance on how optimization might best be applied to crystal-growth problems, and what parameters and factors might most profitably be explored to accelerate and achieve success.

Optimization of crystallization conditions for biological macromolecules

PubMed Central

McPherson, Alexander; Cudney, Bob

2014-01-01

For the successful X-ray structure determination of macromolecules, it is first necessary to identify, usually by matrix screening, conditions that yield some sort of crystals. Initial crystals are frequently microcrystals or clusters, and often have unfavorable morphologies or yield poor diffraction intensities. It is therefore generally necessary to improve upon these initial conditions in order to obtain better crystals of sufficient quality for X-ray data collection. Even when the initial samples are suitable, often marginally, refinement of conditions is recommended in order to obtain the highest quality crystals that can be grown. The quality of an X-ray structure determination is directly correlated with the size and the perfection of the crystalline samples; thus, refinement of conditions should always be a primary component of crystal growth. The improvement process is referred to as optimization, and it entails sequential, incremental changes in the chemical parameters that influence crystallization, such as pH, ionic strength and precipitant concentration, as well as physical parameters such as temperature, sample volume and overall methodology. It also includes the application of some unique procedures and approaches, and the addition of novel components such as detergents, ligands or other small molecules that may enhance nucleation or crystal development. Here, an attempt is made to provide guidance on how optimization might best be applied to crystal-growth problems, and what parameters and factors might most profitably be explored to accelerate and achieve success. PMID:25372810

Single-crystalline chromium silicide nanowires and their physical properties.

PubMed

Hsu, Han-Fu; Tsai, Ping-Chen; Lu, Kuo-Chang

2015-01-01

In this work, chromium disilicide nanowires were synthesized by chemical vapor deposition (CVD) processes on Si (100) substrates with hydrous chromium chloride (CrCl3 · 6H2O) as precursors. Processing parameters, including the temperature of Si (100) substrates and precursors, the gas flow rate, the heating time, and the different flow gas of reactions were varied and studied; additionally, the physical properties of the chromium disilicide nanowires were measured. It was found that single-crystal CrSi2 nanowires with a unique morphology were grown at 700°C, while single-crystal Cr5Si3 nanowires were grown at 750°C in reducing gas atmosphere. The crystal structure and growth direction were identified, and the growth mechanism was proposed as well. This study with magnetism, photoluminescence, and field emission measurements demonstrates that CrSi2 nanowires are attractive choices for future applications in magnetic storage, photovoltaic, and field emitters.

Observation of three-component fermions in the topological semimetal molybdenum phosphide.

PubMed

Lv, B Q; Feng, Z-L; Xu, Q-N; Gao, X; Ma, J-Z; Kong, L-Y; Richard, P; Huang, Y-B; Strocov, V N; Fang, C; Weng, H-M; Shi, Y-G; Qian, T; Ding, H

2017-06-29

In quantum field theory, Lorentz invariance leads to three types of fermion-Dirac, Weyl and Majorana. Although the existence of Weyl and Majorana fermions as elementary particles in high-energy physics is debated, all three types of fermion have been proposed to exist as low-energy, long-wavelength quasiparticle excitations in condensed-matter systems. The existence of Dirac and Weyl fermions in condensed-matter systems has been confirmed experimentally, and that of Majorana fermions is supported by various experiments. However, in condensed-matter systems, fermions in crystals are constrained by the symmetries of the 230 crystal space groups rather than by Lorentz invariance, giving rise to the possibility of finding other types of fermionic excitation that have no counterparts in high-energy physics. Here we use angle-resolved photoemission spectroscopy to demonstrate the existence of a triply degenerate point in the electronic structure of crystalline molybdenum phosphide. Quasiparticle excitations near a triply degenerate point are three-component fermions, beyond the conventional Dirac-Weyl-Majorana classification, which attributes Dirac and Weyl fermions to four- and two-fold degenerate points, respectively. We also observe pairs of Weyl points in the bulk electronic structure of the crystal that coexist with the three-component fermions. This material thus represents a platform for studying the interplay between different types of fermions. Our experimental discovery opens up a way of exploring the new physics of unconventional fermions in condensed-matter systems.

Observation of three-component fermions in the topological semimetal molybdenum phosphide

NASA Astrophysics Data System (ADS)

Lv, B. Q.; Feng, Z.-L.; Xu, Q.-N.; Gao, X.; Ma, J.-Z.; Kong, L.-Y.; Richard, P.; Huang, Y.-B.; Strocov, V. N.; Fang, C.; Weng, H.-M.; Shi, Y.-G.; Qian, T.; Ding, H.

2017-06-01

In quantum field theory, Lorentz invariance leads to three types of fermion—Dirac, Weyl and Majorana. Although the existence of Weyl and Majorana fermions as elementary particles in high-energy physics is debated, all three types of fermion have been proposed to exist as low-energy, long-wavelength quasiparticle excitations in condensed-matter systems. The existence of Dirac and Weyl fermions in condensed-matter systems has been confirmed experimentally, and that of Majorana fermions is supported by various experiments. However, in condensed-matter systems, fermions in crystals are constrained by the symmetries of the 230 crystal space groups rather than by Lorentz invariance, giving rise to the possibility of finding other types of fermionic excitation that have no counterparts in high-energy physics. Here we use angle-resolved photoemission spectroscopy to demonstrate the existence of a triply degenerate point in the electronic structure of crystalline molybdenum phosphide. Quasiparticle excitations near a triply degenerate point are three-component fermions, beyond the conventional Dirac-Weyl-Majorana classification, which attributes Dirac and Weyl fermions to four- and two-fold degenerate points, respectively. We also observe pairs of Weyl points in the bulk electronic structure of the crystal that coexist with the three-component fermions. This material thus represents a platform for studying the interplay between different types of fermions. Our experimental discovery opens up a way of exploring the new physics of unconventional fermions in condensed-matter systems.

Crystal structure and conformational analysis of s-cis-(acetylacetonato)(ethylenediamine-N,N'-diacetato)-chromium(III): development of vibrationally optimized force field (VOFF).

PubMed

Choi, Jong-Ha; Niketić, Svetozar R; Djordjević, Ivana; Clegg, William; Harrington, Ross W

2012-05-01

The crystal structure of [Cr(edda)(acac)] (edda = ethylediamine-N,N'-diacetate; acac = acetylacetonato) has been determined by a single crystal X-ray diffraction study at 150 K. The chromium ion is in a distorted octahedral environment coordinated by two N and two O atoms of chelating edda and two O atoms of acac, resulting in s-cis configuration. The complex crystallizes in the space group P2(1)/c of the monoclinic system in a cell of dimensions a = 10.2588(9), b = 15.801(3), c = 8.7015(11) Å, β =101.201(9)° and Z = 4. The mean Cr-N(edda), Cr-O(edda) and Cr-O(acac) bond distances are 2.0829(14), 1.9678(11) and 1.9477(11) Å while the angles O-Cr-O of edda and O-Cr-O of acac are 171.47(5) and 92.72(5)°, respectively. The crystal structure is stabilized by N-H···O hydrogen bonds linking [Cr(edda)(acac)] molecules in distinct linear strands. The visible electronic and IR spectroscopic properties are also discussed. An improved, physically more realistic force field, Vibrationally Optimized Force Field (VOFF), capable of reproducing structural and vibrational properties of [Cr(edda)(acac)] was developed and its transferability demonstrated on selected chromium(III) complexes with similar ligands.

Salt or cocrystal of salt? Probing the nature of multicomponent crystal forms with infrared spectroscopy

NASA Astrophysics Data System (ADS)

da Silva, Cameron Capeletti; Guimarães, Freddy Fernandes; Ribeiro, Leandro; Martins, Felipe Terra

2016-10-01

The recognition of the nature of a multicomponent crystal form (solvate, salt, cocrystal or cocrystal of salt) is of great importance for pharmaceutical industry because it is directly related to the performance of a pharmaceutical ingredient, since there is interdependence between the structure, its energy and its physical properties. In this context, here we have identified the nature of multicomponent crystal forms of the anti-HIV drug lamivudine with mandelic acid through infrared spectroscopy. These investigated crystal forms were the known S-mandelic acid cocrystal of lamivudine R-mandelate trihydrate (1), a cocrystal of salt, and lamivudine R-mandelate (2), a salt. This approach also supports the identification and distinction of both ionized and unionized forms of mandelic acid in the infrared spectrum of 1. In this way, infrared spectroscopy can be useful to distinguish a cocrystal of salt from either salt or cocrystal forms. In the course of this study, for the first time we have also characterized and determined the crystal structure of R-mandelic acid cocrystal of sodium R-mandelate (3).

Evaluation of structural vacancies for 1/1-Al-Re-Si approximant crystals by positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Yamada, K.; Suzuki, H.; Kitahata, H.; Matsushita, Y.; Nozawa, K.; Komori, F.; Yu, R. S.; Kobayashi, Y.; Ohdaira, T.; Oshima, N.; Suzuki, R.; Takagiwa, Y.; Kimura, K.; Kanazawa, I.

2018-01-01

The size of structural vacancies and structural vacancy density of 1/1-Al-Re-Si approximant crystals with different Re compositions were evaluated by positron annihilation lifetime and Doppler broadening measurements. Incident positrons were found to be trapped at the monovacancy-size open space surrounded by Al atoms. From a previous analysis using the maximum entropy method and Rietveld method, such an open space is shown to correspond to the centre of Al icosahedral clusters, which locates at the vertex and body centre. The structural vacancy density of non-metallic Al73Re17Si10 was larger than that of metallic Al73Re15Si12. The observed difference in the structural vacancy density reflects that in bonding nature and may explain that in the physical properties of the two samples.

Practical quantum mechanics-based fragment methods for predicting molecular crystal properties.

PubMed

Wen, Shuhao; Nanda, Kaushik; Huang, Yuanhang; Beran, Gregory J O

2012-06-07

Significant advances in fragment-based electronic structure methods have created a real alternative to force-field and density functional techniques in condensed-phase problems such as molecular crystals. This perspective article highlights some of the important challenges in modeling molecular crystals and discusses techniques for addressing them. First, we survey recent developments in fragment-based methods for molecular crystals. Second, we use examples from our own recent research on a fragment-based QM/MM method, the hybrid many-body interaction (HMBI) model, to analyze the physical requirements for a practical and effective molecular crystal model chemistry. We demonstrate that it is possible to predict molecular crystal lattice energies to within a couple kJ mol(-1) and lattice parameters to within a few percent in small-molecule crystals. Fragment methods provide a systematically improvable approach to making predictions in the condensed phase, which is critical to making robust predictions regarding the subtle energy differences found in molecular crystals.

Out-of-equilibrium processes in suspensions of oppositely charged colloids: liquid-to-crystal nucleation and gel formation

NASA Astrophysics Data System (ADS)

Sanz, Eduardo

2009-03-01

We study the kinetics of the liquid-to-crystal transformation and of gel formation in colloidal suspensions of oppositely charged particles. We analyse, by means of both computer simulations and experiments, the evolution of a fluid quenched to a state point of the phase diagram where the most stable state is either a homogeneous crystalline solid or a solid phase in contact with a dilute gas. On the one hand, at high temperatures and high packing fractions, close to an ordered-solid/disordered-solid coexistence line, we find that the fluid-to-crystal pathway does not follow the minimum free energy route. On the other hand, a quench to a state point far from the ordered-crystal/disordered-crystal coexistence border is followed by a fluid-to-solid transition through the minimum free energy pathway. At low temperatures and packing fractions we observe that the system undergoes a gas-liquid spinodal decomposition that, at some point, arrests giving rise to a gel-like structure. Both our simulations and experiments suggest that increasing the interaction range favors crystallization over vitrification in gel-like structures. [4pt] In collaboration with Chantal Valeriani, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands and SUPA, School of Physics, University of Edinburgh, JCMB King's Buildings, Mayfield Road, Edinburgh EH9 3JZ, UK; Teun Vissers, Andrea Fortini, Mirjam E. Leunissen, and Alfons van Blaaderen, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University; Daan Frenke, FOM Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands and Department of Chemistry, University of Cambridge, Lensfield Road, CB2 1EW, Cambridge, UK; and Marjolein Dijkstra, Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University.

Crystal Structural Effect of AuCu Alloy Nanoparticles on Catalytic CO Oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhan, Wangcheng; Wang, Jinglin; Wang, Haifeng

2017-06-07

Controlling the physical and chemical properties of alloy nanoparticles (NPs) is an important approach to optimize NP catalysis. Unlike other tuning knobs, such as size, shape, and composition, crystal structure has received limited attention and not been well understood for its role in catalysis. This deficiency is mainly due to the difficulty in synthesis and fine-tuning of the NPs’ crystal structure. Here, Exemplifying by AuCu alloy NPs with face centered cubic (fcc) and face centered tetragonal (fct) structure, we demonstrate a remarkable difference in phase segregation and catalytic performance depending on the crystal structure. During the thermal treatment in air,more » the Cu component in fcc-AuCu alloy NPs segregates more easily onto the alloy surface as compared to that in fct-AuCu alloy NPs. As a result, after annealing at 250 °C in air for 1 h, the fcc- and fct-AuCu alloy NPs are phase transferred into Au/CuO and AuCu/CuO core/shell structures, respectively. More importantly, this variation in heterostructures introduces a significant difference in CO adsorption on two catalysts, leading to a largely enhanced catalytic activity of AuCu/CuO NP catalyst for CO oxidation. Furthermore, the same concept can be extended to other alloy NPs, making it possible to fine-tune NP catalysis for many different chemical reactions.« less

Alkyltributylphosphonium chloride ionic liquids: synthesis, physicochemical properties and crystal structure.

PubMed

Adamová, Gabriela; Gardas, Ramesh L; Nieuwenhuyzen, Mark; Puga, Alberto V; Rebelo, Luís Paulo N; Robertson, Allan J; Seddon, Kenneth R

2012-07-21

A series of alkyltributylphosphonium chloride ionic liquids, prepared from tributylphosphine and the respective 1-chloroalkane, C(n)H(2n+1)Cl (where n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12 or 14), is reported. This work is a continuation of an extended series of tetraalkylphosphonium ionic liquids, where the focus is on the variability of n and its impact on the physical properties, such as melting points/glass transitions, thermal stability, density and viscosity. Experimental density and viscosity data were interpreted using QPSR and group contribution methods and the crystal structure of propyl(tributyl)phosphonium chloride is detailed.

Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages

PubMed Central

2017-01-01

The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal–organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of a cage molecule, CC3, in a systematic way by introducing methyl groups into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure–energy landscape of a CC15-R/CC3-S cocrystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy–structure–function maps. PMID:28776015

Giant enhancement of second harmonic generation in nonlinear photonic crystals with distributed Bragg reflector mirrors.

PubMed

Ren, Ming-Liang; Li, Zhi-Yuan

2009-08-17

We theoretically investigate second harmonic generation (SHG) in one-dimensional multilayer nonlinear photonic crystal (NPC) structures with distributed Bragg reflector (DBR) as mirrors. The NPC structures have periodic modulation on both the linear and second-order susceptibility. Three major physical mechanisms, quasi-phase matching (QPM) effect, slow light effect at photonic band gap edges, and cavity effect induced by DBR mirrors can be harnessed to enhance SHG. Selection of appropriate structural parameters can facilitate coexistence of these mechanisms to act collectively and constructively to create very high SHG conversion efficiency with an enhancement by up to seven orders of magnitude compared with the ordinary NPC where only QPM works. (c) 2009 Optical Society of America

Allowing for crystalline structure effects in Geant4

DOE PAGES

Bagli, Enrico; Asai, Makoto; Dotti, Andrea; ...

2017-03-24

In recent years, the Geant4 toolkit for the Monte Carlo simulation of radiation with matter has seen large growth in its divers user community. A fundamental aspect of a successful physics experiment is the availability of a reliable and precise simulation code. Geant4 currently does not allow for the simulation of particle interactions with anything other than amorphous matter. To overcome this limitation, the GECO (GEant4 Crystal Objects) project developed a general framework for managing solid-state structures in the Geant4 kernel and validate it against experimental data. As a result, accounting for detailed geometrical structures allows, for example, simulation ofmore » diffraction from crystal planes or the channeling of charged particle.« less

Dynamics of topological solitons, knotted streamlines, and transport of cargo in liquid crystals

NASA Astrophysics Data System (ADS)

Sohn, Hayley R. O.; Ackerman, Paul J.; Boyle, Timothy J.; Sheetah, Ghadah H.; Fornberg, Bengt; Smalyukh, Ivan I.

2018-05-01

Active colloids and liquid crystals are capable of locally converting the macroscopically supplied energy into directional motion and promise a host of new applications, ranging from drug delivery to cargo transport at the mesoscale. Here we uncover how topological solitons in liquid crystals can locally transform electric energy to translational motion and allow for the transport of cargo along directions dependent on frequency of the applied electric field. By combining polarized optical video microscopy and numerical modeling that reproduces both the equilibrium structures of solitons and their temporal evolution in applied fields, we uncover the physical underpinnings behind this reconfigurable motion and study how it depends on the structure and topology of solitons. We show that, unexpectedly, the directional motion of solitons with and without the cargo arises mainly from the asymmetry in rotational dynamics of molecular ordering in liquid crystal rather than from the asymmetry of fluid flows, as in conventional active soft matter systems.

Physics and Chemistry of Earth Materials

NASA Astrophysics Data System (ADS)

Navrotsky, Alexandra

1994-11-01

Stressing the fundamental solid state behavior of minerals, and emphasizing both theory and experiment, this text surveys the physics and chemistry of earth materials. The author begins with a systematic tour of crystal chemistry of both simple and complex structures (with completely new structural drawings) and discusses how to obtain structural and thermodynamic information experimentally. Dr. Navrotsky also reviews the quantitative concepts of chemical bonding--band theory, molecular orbit and ionic models. She then covers physical properties and relates microscopic features to macroscopic thermodynamic behavior and treats high pressure phase transitions, amorphous materials and solid state reactions. The author concludes with a look at the interface between mineral physics and materials science. Highly illustrated throughout, this book fills the gap between undergraduate texts and specialized review volumes and is appropriate for students and researchers in earth science and materials science.

Characterization of calcium carbonate crystals in pigeon yolk sacs with different incubation times.

PubMed

Song, Juan; Cheng, Haixia; Shen, Xinyu; Hu, Jingxiao; Tong, Hua

2014-05-01

Calcium carbonate crystals are known to form in the yolk sacs of fertile pigeon eggs at late stages of incubation. The composition and structure of these crystals were investigated, the crystallization environment was inspected, and the physical chemistry constants of the yolk fluid were determined through the incubation period. Polarized light microscopy was used to observe the generation and distribution of calcium carbonate crystals in the yolk sac. In addition, X-ray diffraction was employed to analyze the composition and crystal phase of the yolk sac. A decalcification and deproteination method was established to analyze the ultrastructure and composition of the crystals, as well as the internal relationship between inorganic and organic phases of the crystals. Additionally, scanning electron microscopy, transmission electron microscopy, X-ray energy dispersive spectroscopy, and Fourier transform infrared spectroscopy were used to evaluate the characteristics of the crystals. Our results demonstrated that the calcium carbonate crystals were mainly composed of vaterite and calcite, with vaterite being the major component. Vaterite, a type of biomaterial generated by an organic template control, presented as a concentric hierarchical spherical structure. The organic nature of the biomaterial prevented vaterite from transforming into calcite, which is more thermodynamically stable than vaterite. Additionally, the configuration, size, and aggregation of vaterite were also mediated by the organic template. This bio-vaterite was found during the incubation period and is valuable in calcium transport during embryonic development. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of structural imperfection on gelatinization characteristics of amylopectin starches with A- and B-type crystallinity.

PubMed

Genkina, Natalia K; Wikman, Jeanette; Bertoft, Eric; Yuryev, Vladimir P

2007-07-01

The aim of the present work was to investigate the effect of physical structures on the properties of starch granules. Starches with a high amylopectin content possessing A- and B-type crystallinity were chosen for the study. The gelatinization temperature decreased in the following order: maize (A) > potato (B) > wheat (A) > barley (A), which did not reflect a correlation with the type of crystallinity. Low values of gelatinization temperature were accompanied with high free surface energy of the crystallites. It is proposed that these data are caused by different types of imperfections in starch crystals. Annealing resulted in an enhancement of the gelatinization temperature and a decrease of the free surface energy of the crystallites for all starches reflecting a partial improvement of crystalline perfection. A limited acid hydrolysis (lintnerization) of the starches decreased the gelatinization temperature because of a partial disruption of the crystalline lamellae and an increase of the amount of defects on the edges of the crystallites. Annealing of the lintnerized starches improved the structure of maize and potato starch, giving them similar structural and physicochemical parameters, which was opposite the behavior of the annealed sample from wheat. The possible nature of removable and nonremovable defects inside the crystalline region of the starch granules is discussed. It is concluded that, besides the allomorphic A- and B-types of crystal packing, physical defects in the crystals possess a major impact on starch gelatinization.

Growth of zinc selenide single crystals by physical vapor transport in microgravity

NASA Technical Reports Server (NTRS)

Rosenberger, Franz

1993-01-01

The goals of this research were the optimization of growth parameters for large (20 mm diameter and length) zinc selenide single crystals with low structural defect density, and the development of a 3-D numerical model for the transport rates to be expected in physical vapor transport under a given set of thermal and geometrical boundary conditions, in order to provide guidance for an advantageous conduct of the growth experiments. In the crystal growth studies, it was decided to exclusively apply the Effusive Ampoule PVT technique (EAPVT) to the growth of ZnSe. In this technique, the accumulation of transport-limiting gaseous components at the growing crystal is suppressed by continuous effusion to vacuum of part of the vapor contents. This is achieved through calibrated leaks in one of the ground joints of the ampoule. Regarding the PVT transport rates, a 3-D spectral code was modified. After introduction of the proper boundary conditions and subroutines for the composition-dependent transport properties, the code reproduced the experimentally determined transport rates for the two cases with strongest convective flux contributions to within the experimental and numerical error.

Critical detonation thickness in vapor-deposited hexanitroazobenzene (HNAB) films with different preparation conditions

NASA Astrophysics Data System (ADS)

Tappan, Alexander; Knepper, Robert; Marquez, Michael; Ball, J.; Miller, Jill

2013-06-01

At Sandia National Laboratories, we have coined the term ``microenergetics'' to describe sub-millimeter energetic material studies aimed at gaining knowledge of combustion and detonation behavior at the mesoscale. Films of the high explosive hexanitroazobenzene (HNAB) have been deposited through physical vapor deposition. HNAB deposits in an amorphous state that crystallizes over time and modest heating accelerates this crystallization. HNAB films were prepared under different crystallization temperatures, and characterized with surface profilometry and scanning electron microscopy. The critical detonation thickness for HNAB at different crystallization conditions was determined in a configuration where charge width was large compared to film thickness, and thus side losses did not play a role in detonation propagation. The results of these experiments will be discussed in the context of small sample geometry, deposited film morphology, crystal structure, and density.

High-resolution electron microscopy and its applications.

PubMed

Li, F H

1987-12-01

A review of research on high-resolution electron microscopy (HREM) carried out at the Institute of Physics, the Chinese Academy of Sciences, is presented. Apart from the direct observation of crystal and quasicrystal defects for some alloys, oxides, minerals, etc., and the structure determination for some minute crystals, an approximate image-contrast theory named pseudo-weak-phase object approximation (PWPOA), which shows the image contrast change with crystal thickness, is described. Within the framework of PWPOA, the image contrast of lithium ions in the crystal of R-Li2Ti3O7 has been observed. The usefulness of diffraction analysis techniques such as the direct method and Patterson method in HREM is discussed. Image deconvolution and resolution enhancement for weak-phase objects by use of the direct method are illustrated. In addition, preliminary results of image restoration for thick crystals are given.

Magmatic structures in the Krkonoše Jizera Plutonic Complex, Bohemian Massif: evidence for localized multiphase flow and small-scale thermal mechanical instabilities in a granitic magma chamber

NASA Astrophysics Data System (ADS)

Žák, Jiří; Klomínský, Josef

2007-08-01

The present paper examines magmatic structures in the Jizera and Liberec granites of the Krkonoše-Jizera Plutonic Complex, Bohemian Massif. The magmatic structures are here interpreted to preserve direct field evidence for highly localized magma flow and other processes in crystal-rich mushes, and to capture the evolution of physical processes in an ancient granitic magma chamber. We propose that after chamber-wide mixing and hybridization, as suggested by recent petrological studies, laminar magma flow became highly localized to weaker channel-like domains within the higher-strength crystal framework. Mafic schlieren formed at flow rims, and their formation presumably involved gravitational settling and velocity gradient flow sorting coupled with interstitial melt escape. Local thermal or compositional convection may have resulted in the formation of vertical schlieren tubes and ladder dikes whereas subhorizontal tubes or channels formed during flow driven by lateral gradients in magma pressure. After the cessation or deceleration of channel flow, gravity-driven processes (settling of crystals and enclaves, gravitational differentiation, development of downward dripping instabilities), accompanied by compaction, filter pressing and melt segregation, dominated in the crystal mush within the flow channels. Subsequently, magmatic folds developed in schlieren layers and the magma chamber recorded complex, late magmatic strains at high magma crystallinities. Late-stage magma pulsing into localized submagmatic cracks represents the latest events of magmatic history of the chamber prior to its final crystallization. We emphasize that the most favorable environments for the formation and preservation of magmatic structures, such as those hosted in the Jizera and Liberec granites, are slowly cooling crystal-rich mushes. Therefore, where preserved in plutons, these structures may lend strong support for a "mush model" of magmatic systems.

Crystal structure of an orthomyxovirus matrix protein reveals mechanisms for self-polymerization and membrane association.

PubMed

Zhang, Wenting; Zheng, Wenjie; Toh, Yukimatsu; Betancourt-Solis, Miguel A; Tu, Jiagang; Fan, Yanlin; Vakharia, Vikram N; Liu, Jun; McNew, James A; Jin, Meilin; Tao, Yizhi J

2017-08-08

Many enveloped viruses encode a matrix protein. In the influenza A virus, the matrix protein M1 polymerizes into a rigid protein layer underneath the viral envelope to help enforce the shape and structural integrity of intact viruses. The influenza virus M1 is also known to mediate virus budding as well as the nuclear export of the viral nucleocapsids and their subsequent packaging into nascent viral particles. Despite extensive studies on the influenza A virus M1 (FLUA-M1), only crystal structures of its N-terminal domain are available. Here we report the crystal structure of the full-length M1 from another orthomyxovirus that infects fish, the infectious salmon anemia virus (ISAV). The structure of ISAV-M1 assumes the shape of an elbow, with its N domain closely resembling that of the FLUA-M1. The C domain, which is connected to the N domain through a flexible linker, is made of four α-helices packed as a tight bundle. In the crystal, ISAV-M1 monomers form infinite 2D arrays with a network of interactions involving both the N and C domains. Results from liposome flotation assays indicated that ISAV-M1 binds membrane via electrostatic interactions that are primarily mediated by a positively charged surface loop from the N domain. Cryoelectron tomography reconstruction of intact ISA virions identified a matrix protein layer adjacent to the inner leaflet of the viral membrane. The physical dimensions of the virion-associated matrix layer are consistent with the 2D ISAV-M1 crystal lattice, suggesting that the crystal lattice is a valid model for studying M1-M1, M1-membrane, and M1-RNP interactions in the virion.

Redox-controlled potassium intercalation into two polyaromatic hydrocarbon solids

NASA Astrophysics Data System (ADS)

Romero, F. Denis; Pitcher, M. J.; Hiley, C. I.; Whitehead, G. F. S.; Kar, S.; Ganin, A. Y.; Antypov, D.; Collins, C.; Dyer, M. S.; Klupp, G.; Colman, R. H.; Prassides, K.; Rosseinsky, M. J.

2017-07-01

Alkali metal intercalation into polyaromatic hydrocarbons (PAHs) has been studied intensely after reports of superconductivity in a number of potassium- and rubidium-intercalated materials. There are, however, no reported crystal structures to inform our understanding of the chemistry and physics because of the complex reactivity of PAHs with strong reducing agents at high temperature. Here we present the synthesis of crystalline K2Pentacene and K2Picene by a solid-solid insertion protocol that uses potassium hydride as a redox-controlled reducing agent to access the PAH dianions, and so enables the determination of their crystal structures. In both cases, the inserted cations expand the parent herringbone packings by reorienting the molecular anions to create multiple potassium sites within initially dense molecular layers, and thus interact with the PAH anion π systems. The synthetic and crystal chemistry of alkali metal intercalation into PAHs differs from that into fullerenes and graphite, in which the cation sites are pre-defined by the host structure.

Effect of Sintering Temperature to Physical, Magnetic Properties and Crystal Structure on Permanent Magnet BaFe12O19 Prepared From Mill Scale

NASA Astrophysics Data System (ADS)

Ramlan; Muljadi; Sardjono, Priyo; Gulo, Fakhili; Setiabudidaya, Dedi

2017-07-01

Permanent magnet of Barium hexa Ferrite with formula BaFe12O19 has been made by metallurgy powder method from raw materials : Barium carbonate (BaCO3 E-merck) and Iron Oxide (Fe2O3 from mill scale). Both of raw materials have been mixed with stoichiometry composition by using a ball mill for 24 hours. The fine powder obtained from milling process was formed by using a hydraulic press at pressure 50 MPa and continued with sintering process. The sintering temperature was varied : 1150°C, 1200°C, 1250°C and 1300°C with holding time for 1 hour. The sintered samples were characterized such as : physical properties (bulk density, porosity and shrinkage), magnetic properties (flux density, remanence, coercivity and magnetic saturation) by using VSM and crystal structure by using XRD. According characterization results show that the crystal structure of BaFe12O19 does not change after sintering process, but the grain size tends to increase. The optimum condition is achieved at temperature 1250°C, and at this condition, the sample has characterization such as : bulk density = 4.35 g/cm3, porosity = 1.03% and firing shrinkage = 11.63%, flux density = 681.1 Gauss, remanence (σr) = 20.78 emu/g, coercivity (Hc) = 2058 Oe and magnetic saturation (σs) 45.16 emu/g.

Elasticity and dislocation inelasticity of crystals

NASA Astrophysics Data System (ADS)

Nikanorov, S. P.; Kardashev, B. K.

The use of methods of physical acoustics for studying the elasticity and dislocation inelasticity of crystals is discussed, as is the application of the results of such studies to the analysis of interatomic and lattice defect interactions. The analysis of the potential functions determining the energy of interatomic interactions is based on an analysis of the elastic properties of crystals over a wide temperature range. The data on the dislocation structure and the interaction between dislocations and point defects are obtained from a study of inelastic effects. Particular attention is given to the relationship between microplastic effects under conditions of elastic oscillations and the initial stage of plastic deformation.

EDITORIAL: Photonic Crystal Devices

NASA Astrophysics Data System (ADS)

Bhattacharya, Pallab K.

2007-05-01

The engineering of electromagnetic modes at optical frequencies in artificial dielectric structures with periodic and random variation of the refractive index, enabling control of the radiative properties of the materials and photon localization, was first proposed independently by Yablonovitch and John in 1987. It is possible to control the flow of light in the periodic dielectric structures, known as photonic crystals (PC). As light waves scatter within the photonic crystal, destructive interference cancels out light of certain wavelengths, thereby forming a photonic bandgap, similar to the energy bandgap for electron waves in a semiconductor. Photons whose energies lie within the gap cannot propagate through the periodic structure. This property can be used to make a low-loss cavity. If a point defect, such as one or more missing periods, is introduced into the periodic structure a region is obtained within which the otherwise forbidden wavelengths can be locally trapped. This property can be used to realize photonic microcavities. Similarly, a line of defects can serve as a waveguide. While the realization of three-dimensional (3D) photonic crystals received considerable attention initially, planar two-dimensional (2D) structures are currently favoured because of their relative ease of fabrication. 2D photonic crystal structures provide most of the functionality of 3D structures. These attributes have generated worldwide research and development of sub-μm and μm size active and passive photonic devices such as single-mode and non- classical light sources, guided wave devices, resonant cavity detection, and components for optical communication. More recently, photonic crystal guided wave devices are being investigated for application in microfludic and biochemical sensing. Photonic crystal devices have been realized with bulk, quantum well and quantum dot active regions. The Cluster of articles in this issue of Journal of Physics D: Applied Physics provides a glimpse of some of the most recent advances in the application of photonic crystals. The modelling of PC defect-mode cavities are described by Zhou et al. Ye and co-authors describe the concept and realization of a novel 3D silicon-based spiral PC. It is, in fact, the only article on 3D PCs. The design and realization of ultra-high Q heterostructure PC nanocavities are described by Song and co-authors. The concept of self-collimation of light in PCs and its applications are presented by Prather and co-workers. Experimental and numerical studies on the negative refraction related phenomenon in 2D PCs are the subject of the next article by Ozbay and co-authors. The emerging subject of slow light generation, control and propagation in PCs is presented in the next two articles by Baba and Mori and by Krauss. Finally, the progress made in the development of PC microcavity lasers and electrically injected microcavity light emitters and arrays is described, respectively, by O'Brien et al and by Chakravarty et al. It is hoped that readers will get a sense of the exciting developments and the possibilities presented by heterostructure photonic crystals and their devices from reading the articles in this Cluster.

New trends in chemistry and materials science in extremely tight space

DOE PAGES

Song, Yang; Manaa, M. Riad

2012-01-26

Pressure plays a critical role in regulating the structures and properties of materials. Since Percy Bridgeman was recognized by the 1946 Nobel Prize in Physics for his contribution in high-pressure physics, high-pressure research has remained an interdisciplinary scientific frontier with many extraordinary breakthroughs. Over the past decade or so, in particular, high-pressure chemistry and materials research has undergone major advances with the discovery of numerous exotic structures and properties. Furthermore, brand new classes of inorganic materials of unusual stoichiometries and crystal structures, which have a wide range of optical, mechanical, electronic and magnetic properties, have been produced at high pressures.

New trends in chemistry and materials science in extremely tight space

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Yang; Manaa, M. Riad

Pressure plays a critical role in regulating the structures and properties of materials. Since Percy Bridgeman was recognized by the 1946 Nobel Prize in Physics for his contribution in high-pressure physics, high-pressure research has remained an interdisciplinary scientific frontier with many extraordinary breakthroughs. Over the past decade or so, in particular, high-pressure chemistry and materials research has undergone major advances with the discovery of numerous exotic structures and properties. Furthermore, brand new classes of inorganic materials of unusual stoichiometries and crystal structures, which have a wide range of optical, mechanical, electronic and magnetic properties, have been produced at high pressures.

Crystal structure determination of new antimitotic agent bis(p-fluorobenzyl)trisulfide.

PubMed

An, Haoyun; Hu, Xiurong; Gu, Jianming; Chen, Linshen; Xu, Weiming; Mo, Xiaopeng; Xu, Wanhong; Wang, Xiaobo; Xu, Xiao

2008-01-01

The purpose of this research was to investigate the physical characteristics and crystalline structure of bis(p-fluorobenzyl)trisulfide, a new anti-tumor agent. Methods used included X-ray single crystal diffraction, X-ray powder diffraction (XRPD), Fourier-transform infrared (FT-IR) spectroscopy, differential scanning calorimetric (DSC) and thermogravimetric (TG) analyses. The findings obtained with X-ray single crystal diffraction showed that a monoclinic unit cell was a = 12.266(1) A, b = 4.7757(4) A, c = 25.510(1) A, beta = 104.25(1) degrees ; cell volume = 1,448.4(2) A(3), Z = 4, and space group C2/c. The XRPD studies of the four crystalline samples, obtained by recrystallization from four different solvents, indicated that they had the same diffraction patterns. The diffraction pattern stimulated from the crystal structure data is in excellent agreement with the experimental results. In addition, the identical FT-IR spectra of the four crystalline samples revealed absorption bands corresponding to S-S and C-S stretching as well as the characteristic aromatic substitution. Five percent weight loss at 163.3 degrees C was observed when TG was used to study the decomposition process in the temperature range of 20-200 degrees C. DSC also allowed for the determination of onset temperatures at 60.4(1)-60.7(3) degrees C and peak temperatures at 62.1(3)-62.4(3) degrees C for the four crystalline samples studied. The results verified that the single crystal structure shared the same crystal form with the four crystalline samples investigated.

Physical stability of drugs after storage above and below the glass transition temperature: Relationship to glass-forming ability.

PubMed

Alhalaweh, Amjad; Alzghoul, Ahmad; Mahlin, Denny; Bergström, Christel A S

2015-11-10

Amorphous materials are inherently unstable and tend to crystallize upon storage. In this study, we investigated the extent to which the physical stability and inherent crystallization tendency of drugs are related to their glass-forming ability (GFA), the glass transition temperature (Tg) and thermodynamic factors. Differential scanning calorimetry was used to produce the amorphous state of 52 drugs [18 compounds crystallized upon heating (Class II) and 34 remained in the amorphous state (Class III)] and to perform in situ storage for the amorphous material for 12h at temperatures 20°C above or below the Tg. A computational model based on the support vector machine (SVM) algorithm was developed to predict the structure-property relationships. All drugs maintained their Class when stored at 20°C below the Tg. Fourteen of the Class II compounds crystallized when stored above the Tg whereas all except one of the Class III compounds remained amorphous. These results were only related to the glass-forming ability and no relationship to e.g. thermodynamic factors was found. The experimental data were used for computational modeling and a classification model was developed that correctly predicted the physical stability above the Tg. The use of a large dataset revealed that molecular features related to aromaticity and π-π interactions reduce the inherent physical stability of amorphous drugs. Copyright © 2015 Elsevier B.V. All rights reserved.

A combined experimental and in silico characterization to highlight additional structural features and properties of a potentially new drug

NASA Astrophysics Data System (ADS)

Bastos, Isadora T. S.; Costa, Fanny N.; Silva, Tiago F.; Barreiro, Eliezer J.; Lima, Lídia M.; Braz, Delson; Lombardo, Giuseppe M.; Punzo, Francesco; Ferreira, Fabio F.; Barroso, Regina C.

2017-10-01

LASSBio-1755 is a new cycloalkyl-N-acylhydrazone parent compound designed for the development of derivatives with antinociceptive and anti-inflammatory activities. Although single crystal X-ray diffraction has been considered as the golden standard in structure determination, we successfully used X-ray powder diffraction data in the structural determination of new synthesized compounds, in order to overcome the bottle-neck due to the difficulties experienced in harvesting good quality single crystals of the compounds. We therefore unequivocally assigned the relative configuration (E) to the imine double bond and a s-cis conformation of the amide function of the N-acylhydrazone compound. These features are confirmed by a computational analysis performed on the basis of molecular dynamics calculations, which are extended not only to the structural characteristics but also to the analysis of the anisotropic atomic displacement parameters, a further information - missed in a typical powder diffraction analysis. The so inferred data were used to perform additional cycles of refinement and eventually generate a new cif file with additional physical information. Furthermore, crystal morphology prediction was performed, which is in agreement with the experimental images acquired by scanning electron microscopy, thus providing useful information on possible alternative paths for better crystallization strategies.

Glass Forming Ability in Systems with Competing Orderings

NASA Astrophysics Data System (ADS)

Russo, John; Romano, Flavio; Tanaka, Hajime

2018-04-01

Some liquids, if cooled rapidly enough to avoid crystallization, can be frozen into a nonergodic glassy state. The tendency for a material to form a glass when quenched is called "glass-forming ability," and it is of key significance both fundamentally and for materials science applications. Here, we consider liquids with competing orderings, where an increase in the glass-forming ability is signaled by a depression of the melting temperature towards its minimum at triple or eutectic points. With simulations of two model systems where glass-forming ability can be tuned by an external parameter, we are able to interpolate between crystal-forming and glass-forming behavior. We find that the enhancement of the glass-forming ability is caused by an increase in the structural difference between liquid and crystal: stronger competition in orderings towards the melting point minimum makes a liquid structure more disordered (more complex). This increase in the liquid-crystal structure difference can be described by a single adimensional parameter, i.e., the interface energy cost scaled by the thermal energy, which we call the "thermodynamic interface penalty." Our finding may provide a general physical principle for not only controlling the glass-forming ability but also the emergence of glassy behavior of various systems with competing orderings, including orderings of structural, magnetic, electronic, charge, and dipolar origin.

Enhanced oxygen vacancy diffusion in Ta2O5 resistive memory devices due to infinitely adaptive crystal structure

NASA Astrophysics Data System (ADS)

Jiang, Hao; Stewart, Derek A.

2016-04-01

Metal oxide resistive memory devices based on Ta2O5 have demonstrated high switching speed, long endurance, and low set voltage. However, the physical origin of this improved performance is still unclear. Ta2O5 is an important archetype of a class of materials that possess an adaptive crystal structure that can respond easily to the presence of defects. Using first principles nudged elastic band calculations, we show that this adaptive crystal structure leads to low energy barriers for in-plane diffusion of oxygen vacancies in λ phase Ta2O5. Identified diffusion paths are associated with collective motion of neighboring atoms. The overall vacancy diffusion is anisotropic with higher diffusion barriers found for oxygen vacancy movement between Ta-O planes. Coupled with the fact that oxygen vacancy formation energy in Ta2O5 is relatively small, our calculated low diffusion barriers can help explain the low set voltage in Ta2O5 based resistive memory devices. Our work shows that other oxides with adaptive crystal structures could serve as potential candidates for resistive random access memory devices. We also discuss some general characteristics for ideal resistive RAM oxides that could be used in future computational material searches.

Protonation of inorganic 5-Fluorocytosine salts

NASA Astrophysics Data System (ADS)

Souza, Matheus S.; da Silva, Cecília C. P.; Almeida, Leonardo R.; Diniz, Luan F.; Andrade, Marcelo B.; Ellena, Javier

2018-06-01

5-Fluorocytosine (5-FC) has been widely used for the treatment of fungal infections and recently was found to exert an extraordinary antineoplastic activity in gene directed prodrug therapy. However, despite of its intense use, 5-FC exhibits tabletability issues due its physical instability in humid environments, leading to transition from the anhydrous to monohydrate phase. By considering that salt formation is an interesting strategy to overcome this problem, in this paper crystal engineering approach was applied to the supramolecular synthesis of new 5-FC salts with sulfuric, hydrobromic and methanesulfonic inorganic acids. A total of four structures were obtained, namely 5-FC sulfate monohydrate (1:1:1), 5-FC hydrogen sulfate (1:1), 5-FC mesylate (1:1) and 5-FC hydrobromide (1:1), the last one being a polymorphic form of a structure already reported in the literature. These novel salts were structurally characterized by single crystal X-ray diffraction and its supramolecular organization were analyses by Hirshfeld surface analysis. The vibrational behavior was evaluated by Raman spectroscopy and it was found to be consistent with the crystal structures.

Beating the Heat - Fast Scanning Melts Silk Beta Sheet Crystals

NASA Astrophysics Data System (ADS)

Cebe, Peggy; Hu, Xiao; Kaplan, David L.; Zhuravlev, Evgeny; Wurm, Andreas; Arbeiter, Daniela; Schick, Christoph

2013-01-01

Beta-pleated-sheet crystals are among the most stable of protein secondary structures, and are responsible for the remarkable physical properties of many fibrous proteins, such as silk, or proteins forming plaques as in Alzheimer's disease. Previous thinking, and the accepted paradigm, was that beta-pleated-sheet crystals in the dry solid state were so stable they would not melt upon input of heat energy alone. Here we overturn that assumption and demonstrate that beta-pleated-sheet crystals melt directly from the solid state to become random coils, helices, and turns. We use fast scanning chip calorimetry at 2,000 K/s and report the first reversible thermal melting of protein beta-pleated-sheet crystals, exemplified by silk fibroin. The similarity between thermal melting behavior of lamellar crystals of synthetic polymers and beta-pleated-sheet crystals is confirmed. Significance for controlling beta-pleated-sheet content during thermal processing of biomaterials, as well as towards disease therapies, is envisioned based on these new findings.

A multistep single-crystal-to-single-crystal bromodiacetylene dimerization

NASA Astrophysics Data System (ADS)

Hoheisel, Tobias N.; Schrettl, Stephen; Marty, Roman; Todorova, Tanya K.; Corminboeuf, Clémence; Sienkiewicz, Andrzej; Scopelliti, Rosario; Schweizer, W. Bernd; Frauenrath, Holger

2013-04-01

Packing constraints and precise placement of functional groups are the reason that organic molecules in the crystalline state often display unusual physical or chemical properties not observed in solution. Here we report a single-crystal-to-single-crystal dimerization of a bromodiacetylene that involves unusually large atom displacements as well as the cleavage and formation of several bonds. Density functional theory computations support a mechanism in which the dimerization is initiated by a [2 + 1] photocycloaddition favoured by the nature of carbon-carbon short contacts in the crystal structure. The reaction proceeded up to the theoretical degree of conversion without loss of crystallinity, and it was also performed on a preparative scale with good yield. Moreover, it represents the first synthetic pathway to (E)-1,2-dibromo-1,2-diethynylethenes, which could serve as synthetic intermediates for the preparation of molecular carbon scaffolds. Our findings both extend the scope of single-crystal-to-single-crystal reactions and highlight their potential as a synthetic tool for complex transformations.

Nonstoichiometry and luminescent properties of ZnSe crystals grown from the melt at high pressures

NASA Astrophysics Data System (ADS)

Khanh, Tran; Mozhevitina, Elena; Khomyakov, Andrew; Avetisov, Roman; Davydov, Albert; Chegnov, Vladimir; Antonov, Vladimir; Kobeleva, Svetlana; Zhavoronkov, Nikolai; Avetissov, Igor

2017-01-01

50 mm diameter ZnSe crystals have been grown from the melt by a vertical Bridgman technique at 100 atm argon pressure in a graphite crucible. 3D impurities concentration and nonstoichiometry mappings of the grown crystals have been defined by ICP-MS and a direct physic-chemical method, correspondingly. Photoluminescence mapping of the analyzed crystal has been done. It was found out that along the crystal height the nonstoichiometry changed from Se excess over stoichiometrical composition in the cone (bottom) part to Zn excess in the tail (upper) part passing through the stoichiometrical composition in the cylindrical part of the crystal. Metal impurities concentrated in the upper part of the crystal. The gas-forming impurities (H, C, O, N, F) had stochastic distribution but Cl impurity concentrated in the crystal peripheral part (near the crucible walls). It was found out that the as-grown crystal had a single wide PL peal with maximum of 583 nm. A proposal about complex structure luminescent center based on Cl dopant an overstoichiometric Se has been made.

Large grained perovskite solar cells derived from single-crystal perovskite powders with enhanced ambient stability

DOE PAGES

Yen, Hung -Ju; Liang, Po -Wei; Chueh, Chu -Chen; ...

2016-05-25

In this study, we demonstrate the large grained perovskite solar cells prepared from precursor solution comprising single-crystal perovskite powders for the first time. Here, the resultant large grained perovskite thin film possesses negligible physical (structural) gap between each large grain and are highly crystalline as evidenced by its fan-shaped birefringence observed under polarized light, which is very different to the thin film prepared from the typical precursor route (MAI + PbI 2).

Does crystallography need a new name?

DOE PAGES

Argryriou, Dimitri

2017-07-01

The discovery of X-rays and their use in the observation of diffraction from crystals placed crystallography at the forefront of science at the beginning of the last century. The combination of this new tool, together with the emerging understanding of the symmetry of crystals, exposed the locations of atoms in matter and allowed us to start understanding macroscopic properties from an atomic perspective for the first time. These discoveries transformed physics and chemistry bringing to light new scientific fields such as materials science and structural biology.

Does crystallography need a new name?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Argryriou, Dimitri

The discovery of X-rays and their use in the observation of diffraction from crystals placed crystallography at the forefront of science at the beginning of the last century. The combination of this new tool, together with the emerging understanding of the symmetry of crystals, exposed the locations of atoms in matter and allowed us to start understanding macroscopic properties from an atomic perspective for the first time. These discoveries transformed physics and chemistry bringing to light new scientific fields such as materials science and structural biology.

Synthesis of monoclinic IrTe 2 under high pressure and its physical properties

DOE PAGES

Li, X.; Yan, J. -Q.; Singh, D. J.; ...

2015-10-12

In a pressure-temperature (P-T) diagram for synthesizing IrTe 2 compounds, the well-studied trigonal (H) phase with the CdI 2-type structure is stable at low pressures. The superconducting cubic (C) phase can be synthesized under higher temperatures and pressures. A rhombohedral phase with the crystal structure similar to the C phase can be made at ambient pressure; but the phase contains a high concentration of Ir deficiency. Here, we report that a rarely studied monoclinic (M) phase can be stabilized in narrow ranges of pressure and temperature in this P-T diagram. Moreover, the peculiar crystal structure of the M-IrTe 2 eliminatesmore » the tendency to form Ir-Ir dimers found in the H phase. The M phase has been fully characterized by structural determination and measurements of electrical resistivity, thermoelectric power, DC magnetization, and specific heat. These physical properties have been compared with those in the H and C phases of Ir 1-xTe 2. Finally, we present magnetic and transport properties and specific heat of the M-IrTe 2 can be fully justified by calculations with the density-functional theory.« less

Physical Studies of P450–P450 Interactions: Predicting Quaternary Structures of P450 Complexes in Membranes from Their X-ray Crystal Structures

PubMed Central

Reed, James R.; Backes, Wayne L.

2017-01-01

Cytochrome P450 enzymes, which catalyze oxygenation reactions of both exogenous and endogenous chemicals, are membrane bound proteins that require interaction with their redox partners in order to function. Those responsible for drug and foreign compound metabolism are localized primarily in the endoplasmic reticulum of liver, lung, intestine, and other tissues. More recently, the potential for P450 enzymes to exist as supramolecular complexes has been shown by the demonstration of both homomeric and heteromeric complexes. The P450 units in these complexes are heterogeneous with respect to their distribution and function, and the interaction of different P450s can influence P450-specific metabolism. The goal of this review is to examine the evidence supporting the existence of physical complexes among P450 enzymes. Additionally, the review examines the crystal lattices of different P450 enzymes derived from X-ray diffraction data to make assumptions regarding possible quaternary structures in membranes and in turn, to predict how the quaternary structures could influence metabolism and explain the functional effects of specific P450–P450 interactions. PMID:28194112

Crystal structure of Gib2, a signal-transducing protein scaffold associated with ribosomes in Cryptococcus neoformans

NASA Astrophysics Data System (ADS)

Ero, Rya; Dimitrova, Valya Tenusheva; Chen, Yun; Bu, Wenting; Feng, Shu; Liu, Tongbao; Wang, Ping; Xue, Chaoyang; Tan, Suet Mien; Gao, Yong-Gui

2015-03-01

The atypical Gβ-like/RACK1 Gib2 protein promotes cAMP signalling that plays a central role in regulating the virulence of Cryptococcus neoformans. Gib2 contains a seven-bladed β transducin structure and is emerging as a scaffold protein interconnecting signalling pathways through interactions with various protein partners. Here, we present the crystal structure of Gib2 at a 2.2-Å resolution. The structure allows us to analyse the association between Gib2 and the ribosome, as well as to identify the Gib2 amino acid residues involved in ribosome binding. Our studies not only suggest that Gib2 has a role in protein translation but also present Gib2 as a physical link at the crossroads of various regulatory pathways important for the growth and virulence of C. neoformans.

Metal-loaded pollucite-like aluminophosphates: dissymmetrisation of crystal structures and physical properties

NASA Astrophysics Data System (ADS)

Shvanskaya, L. V.; Yakubovich, O. V.; Koshelev, A. V.; Vasiliev, A. N.

2018-02-01

Two aluminophosphate analogues of the mineral pollucite with the general formula Cs2(M,Al)3P3O12 (where M = Cu or Mn) have been synthesized by high-temperature flux and structurally characterized using the single-crystal X-ray diffraction. Both samples crystallize in cubic I4132 space group, Z = 8, with a = 13.5911(5) and a = 13.8544(7) for Cu- and Mn-loaded phases, respectively. Their framework structures are based on the ANA-type topology and exhibit the partial ordering of the metal (M/Al) and phosphorus (P) cations over the tetrahedral sites. The regular changes in cell dimensions and volumes in the row Cs2(Cu,Al)3P3O12→Cs2(Mn,Al)3P3O12 obviously correspond to increasing radii of the transition metal. The crystal chemical analysis of both pollucite-like phases show correlations between the difference in the radii size of tetrahedral cations and the degree of distortion of flexible ANA-type framework due to decreasing of the intertetrahedral angles (T-O-T). Magnetic susceptibility measurements indicate that both compounds are paramagnets in the temperature range of 2-300 K.

The Pythagorean Theorem and the Solid State

ERIC Educational Resources Information Center

Kelly, Brenda S.; Splittgerber, Allan G.

2005-01-01

Packing efficiency and crystal density can be calculated from basic geometric principles employing the Pythagorean theorem, if the unit-cell structure is known. The procedures illustrated have applicability in courses such as general chemistry, intermediate and advanced inorganic, materials science, and solid-state physics.

Relationship between mechanical properties and crystal structure in cocrystals and salt of paracetamol.

PubMed

Ahmed, Hamzah; Shimpi, Manishkumar R; Velaga, Sitaram P

2017-01-01

Objectives were to study mechanical properties of various solid forms of paracetamol and relate to their crystal structures. Paracetamol form I (PRA), its cocrystals with oxalic acid (PRA-OXA) and 4,4-bipyridine (PRA-BPY) and hydrochloride salt (PRA-HCL) were selected. Cocrystals and salt were scaled-up using rational crystallization methods. The resulting materials were subjected to different solid-state characterizations. The powders were sieved and 90-360 µm sieve fraction was considered. These powders were examined by scanning electron microscopy (SEM) and densities were determined. Tablets were made at applied pressures of 35-180 MPa under controlled conditions and the tablet height, diameter and hardness were measured. Tensile strength and porosity of the tablets were estimated using well known models. Crystal structures of these systems were visualized and slip planes were identified. Cocrystal and salt of PRA were physically pure. Sieved powders had comparable morphologies and particle size. The apparent and theoretical densities of powders were similar, but no clear trends were observed. The tensile strengths of these compacts were increased with increasing pressure whereas tabletability decreased in the order oxalic acid > PRA-HCL ≈ PRA-OXA > BPY > PRA-BPY. Tablet tensile strength decreases exponentially with increasing porosity with the exception of PRY-BPY and BPY. Slip plane prediction based on attachment energies may not be independently considered. However, it was possible to explain the improved mechanical properties of powders based on the crystal structure. Cocrystallization and salt formation have introduced structural features that are responsible for improved tableting properties of PRA.

Fluid Physics and Macromolecular Crystal Growth in Microgravity

NASA Technical Reports Server (NTRS)

Pusey, M.; Snell, E.; Judge, R.; Chayen, N.; Boggon, T.

2000-01-01

The molecular structure of biological macromolecules is important in understanding how these molecules work and has direct application to rational drug design for new medicines and for the improvement and development of industrial enzymes. In order to obtain the molecular structure, large, well formed, single macromolecule crystals are required. The growth of macromolecule crystals is a difficult task and is often hampered on the ground by fluid flows that result from the interaction of gravity with the crystal growth process. One such effect is the bulk movement of the crystal through the fluid due to sedimentation. A second is buoyancy driven convection close to the crystal surface. On the ground the crystallization process itself induces both of these flows. Buoyancy driven convection results from density differences between the bulk solution and fluid close to the crystal surface which has been depleted of macromolecules due to crystal growth. Schlieren photograph of a growing lysozyme crystal illustrating a 'growth plume' resulting from buoyancy driven convection. Both sedimentation and buoyancy driven convection have a negative effect on crystal growth and microgravity is seen as a way to both greatly reduce sedimentation and provide greater stability for 'depletion zones' around growing crystals. Some current crystal growth hardware however such as those based on a vapor diffusion techniques, may also be introducing unwanted Marangoni convection which becomes more pronounced in microgravity. Negative effects of g-jitter on crystal growth have also been observed. To study the magnitude of fluid flows around growing crystals we have attached a number of different fluorescent probes to lysozyme molecules. At low concentrations, less than 40% of the total protein, the probes do not appear to effect the crystal growth process. By using these probes we expect to determine not only the effect of induced flows due to crystal growth hardware design but also hope to optimize crystallization hardware so that destructive flows are minimized both on the ground and in microgravity.

Crystallization of Polymers in Confined Environments: Structural Development of Semi-crystalline Polymer-Layered Silicate Nanocomposites

NASA Astrophysics Data System (ADS)

Vaia, Richard A.; Lincoln, Derek M.; Wang, Zhi-Gang; Hsiao, Benjamin S.; Krishnamoorti, Ramanan

2000-03-01

Over the last decade, the utility of ultrafine dispersions of inorganic nanoparticles to enhance polymer performance and function as precursors to form self-passivating / self-healing inorganic coatings on the polymer surface has been established. Before developing the fundamental structure-property relationships though, a detailed understanding of processing / morphology relationships is necessary. As with other multiphase systems exhibiting nano (1-100 nm) and meso (100-500 nm) order (such as biopolymers, block-copolymers, colloidal suspensions, liquid crystals), physical properties ranging from toughness to optical clarity are determined by morphology on various length scales which in turn arise from processing history. This is anticipated to be especially important for blends containing two or more constituents with fundamental structural features on the nanoscale, such as crystal lamellae and aluminosilicate sheets. Small-angle x-ray scattering experiments with synchrotron radiation reveal the presence of ultra-long range (20-60 nm) mesoscopic ordering of the layered silicate in molten polyamide 6-layered silicate nanocomposites. This superstructure of these semi-rigid inorganic sheets provides a confined environment to examine the crystallization of polyamide 6 with traditional bulk characterization techniques. In addition to a change lamellae organization and lamellae size, the presence of the aluminosilicate layers and extent of interfacial interactions (end-tethered v. physiadsorbed chains) substantially alters the nucleation rate, growth kinetics and Brill transition of the crystal phase as revealed by isothermal crystallization experiments monitored in-situ with synchrotron radiation. These exfoliated nanocomposites provide new opportunities to investigate confined polymer crystallization as well as provide insight into the origin of various property enhancements in these systems.

Structural, spectroscopic and electronic properties of hydrogen-bonded water molecules in crystals. Ab initio calculations and experimental data of MC1 2· n(H,D) 2O, M = Sr or Ba

NASA Astrophysics Data System (ADS)

Möller, H.; Niu, J. E.; Lutz, H. D.; Schwarz, W. H. E.

1997-12-01

Structural, spectroscopic and electronic properties of (more or less deuterated) water molecules in the crystal fields of SrCl 2·2H 2O, SrCl 2·H 2O and BaCl 2·H 2O, previously investigated by experimental techniques, were calculated by ab initio SCF-MP methods. The H 2O molecules of each compound are asymmetrically surrounded by three adjacent chloride ions, one hydrogen atom being attached to a nearby Cl -, the other less perturbed hydrogen atom bridging the two less near Cl -. The diversity of structural and spectroscopic features found experimentally, for instance the trends from free H 2O to H 2O in BaCl 2·H 2OSrCl 2·H 2OSrCl 2·2H 2O, are well reproduced by the model calculations, which provide the correct assignment and physical interpretation. The differences between the compounds and the asymmetry of the hydrate water molecules can be rationalized with the help of crystal fields. The crystal environment expands the internuclear distances of H 2O by up to 3 pm. The change of vibrational frequencies can be explained qualitatively by only taking the coupling and anharmonicity of the free water molecule and its modified structure in the crystals into account. The infra-red intensities, however, are strongly influenced by the electronic polarization.

Comparing two tetraalkylammonium ionic liquids. II. Phase transitions.

PubMed

Lima, Thamires A; Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C; Ferreira, Fabio F; Costa, Fanny N; Giles, Carlos

2016-06-14

Phase transitions of the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2], were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) measurements, and Raman spectroscopy. XRD and Raman spectra were obtained as a function of temperature at atmospheric pressure, and also under high pressure at room temperature using a diamond anvil cell (DAC). [N1444][NTf2] experiences glass transition at low temperature, whereas [N1114][NTf2] crystallizes or not depending on the cooling rate. Both the ionic liquids exhibit glass transition under high pressure. XRD and low-frequency Raman spectra provide a consistent physical picture of structural ordering-disordering accompanying the thermal events of crystallization, glass transition, cold crystallization, pre-melting, and melting. Raman spectra in the high-frequency range of some specific cation and anion normal modes reveal conformational changes of the molecular structures along phase transitions.

Vapor-Deposited Glasses with Long-Range Columnar Liquid Crystalline Order

DOE PAGES

Gujral, Ankit; Gomez, Jaritza; Ruan, Shigang; ...

2017-10-04

Anisotropic molecular packing, particularly in highly ordered liquid crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized glassy solids of discotic liquid crystalline systems. Using grazing incidence X-ray scattering, atomic force microscopy, and UV–vis spectroscopy, we compare three systems: a rectangular columnar liquid crystal, a hexagonal columnar liquid crystal, and a nonmesogen. The packing motifs accessible by vapor deposition are highly organized for the liquid crystalline systems with columns propagating either in-plane or out-of-plane depending upon the substrate temperature during deposition.more » As a result, the structures formed at a given substrate temperature can be understood as resulting from partial equilibration toward the structure of the equilibrium liquid crystal surface during the deposition process.« less

Ideal Weyl points and helicoid surface states in artificial photonic crystal structures.

PubMed

Yang, Biao; Guo, Qinghua; Tremain, Ben; Liu, Rongjuan; Barr, Lauren E; Yan, Qinghui; Gao, Wenlong; Liu, Hongchao; Xiang, Yuanjiang; Chen, Jing; Fang, Chen; Hibbins, Alastair; Lu, Ling; Zhang, Shuang

2018-03-02

Weyl points are the crossings of linearly dispersing energy bands of three-dimensional crystals, providing the opportunity to explore a variety of intriguing phenomena such as topologically protected surface states and chiral anomalies. However, the lack of an ideal Weyl system in which the Weyl points all exist at the same energy and are separated from any other bands poses a serious limitation to the further development of Weyl physics and potential applications. By experimentally characterizing a microwave photonic crystal of saddle-shaped metallic coils, we observed ideal Weyl points that are related to each other through symmetry operations. Topological surface states exhibiting helicoidal structure have also been demonstrated. Our system provides a photonic platform for exploring ideal Weyl systems and developing possible topological devices. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Thermoelectric clathrates of type I.

PubMed

Christensen, Mogens; Johnsen, Simon; Iversen, Bo Brummerstedt

2010-01-28

Thermoelectric clathrates hold significant promise for high temperature applications with zT values exceeding 1.3. The inorganic clathrates have been shown to be both chemically and thermally stable at high temperatures, and high performance can be obtained from both single crystals and processed powders. The clathrates also show excellent compatibility factors in segmented module applications. For a materials chemist it is furthermore of great importance that the clathrates exhibit a very rich chemistry with the ability for substitution of many different elements. This allows delicate tuning of both the crystal structure as well as the physical properties. With all these assets, it is not surprising that clathrates have been intensely investigated in the thermoelectric community during the past decade. The present perspective provides a review of the many studies concerned with the synthesis, crystal structure and thermoelectric properties of clathrates with emphasis on the type I clathrate.

Vapor-Deposited Glasses with Long-Range Columnar Liquid Crystalline Order

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gujral, Ankit; Gomez, Jaritza; Ruan, Shigang

Anisotropic molecular packing, particularly in highly ordered liquid crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized glassy solids of discotic liquid crystalline systems. Using grazing incidence X-ray scattering, atomic force microscopy, and UV–vis spectroscopy, we compare three systems: a rectangular columnar liquid crystal, a hexagonal columnar liquid crystal, and a nonmesogen. The packing motifs accessible by vapor deposition are highly organized for the liquid crystalline systems with columns propagating either in-plane or out-of-plane depending upon the substrate temperature during deposition.more » As a result, the structures formed at a given substrate temperature can be understood as resulting from partial equilibration toward the structure of the equilibrium liquid crystal surface during the deposition process.« less

Towards physical implementation of an optical add-drop multiplexer (OADM) based upon properties of 12-fold photonic quasicrystals

NASA Astrophysics Data System (ADS)

Gauthier, Robert C.; Mnaymneh, Khaled

2005-09-01

The key feature that gives photonic crystals (PhCs) their ability to form photonic band gaps (PBGs) analogous to electronic band gaps of semiconductors is their translation symmetries. In recent years, however, it has been found that structures that possess only rotational symmetries can also have PBGs. In addition, these structures, known as Photonic Quasicrystals (PhQs), have other interesting qualities that set them apart of their translational cousins. One interesting feature is how defect states can be created in PhQs. If the rotational symmetry is disturbed, defect states analogous to defects states that are created in PhCs can be obtained. Simulation results of these defect states and other propagation properties of planar 12-fold photonic quasicrystal patterns, and its physical implementations in Silicon-On-Insulator (SOI) are presented. The main mechanisms required to make any optical multiplexing system is propagation; stop bands and add/drop ports. With the rotationally symmetry of the PhQ causing the stop bands, line defects facilitating propagation and now these specially design defect states acting as add/drop ports, a physical implementation of an OADM can be presented. Theoretical, practical and manufacturing benefits of PhQs are discussed. Simulated transmission plots are shown for various fill factors, dielectric contrast and propagation direction. It is shown that low index waveguides can be produced using the quasi-crystal photonic crystal pattern. Fabrication steps and results are shown.

Structure-property relationships: asymmetric alkylphenyl-substituted anthracene molecules for use in small-molecule solar cells.

PubMed

Kim, Yu Jin; Ahn, Eun Soo; Jang, Sang Hun; An, Tae Kyu; Kwon, Soon-Ki; Chung, Dae Sung; Kim, Yun-Hi; Park, Chan Eon

2015-05-11

Two asymmetric anthracene-based organic molecules, NDHPEA and TNDHPEA, were prepared without or with a thiophene spacer between the anthracene and naphthalene units. These asymmetric oligomers displayed different degrees of coplanarity, as evidenced by differences in the dihedral angles calculated by using DFT. Differential scanning calorimetry and XRD studies were used to probe the crystallization characteristics and molecular packing structures in the active layers. The coplanarity of the molecules in the asymmetric structure significantly affected the crystallization behavior and the formation of crystalline domains in the solid state. The small-molecule crystalline properties were correlated with the device physics by determining the J-V characteristics and hole mobilities of the devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of Solid-State NMR to Reveal Structural Differences in Cefazolin Sodium Pentahydrate from Different Manufacturing Processes

NASA Astrophysics Data System (ADS)

Tian, Ye; Wang, Wei D.; Zou, Wen-Bo; Qian, Jian-Qin; Hu, Chang-Qin

2018-04-01

The solid form of an active pharmaceutical ingredient is important when developing a new chemical entity. A solid understanding of the crystal structure and morphology that affect the mechanical and physical characteristics of pharmaceutical powders determines the manufacturing process. Solid-state NMR, thermogravimetric analysis, X-ray diffraction, and Fourier-transform infrared spectroscopy were combined with theoretical calculation to investigate different crystal packings of α-cefazolin sodium from three different vendors and conformational polymorphism was identified to exist in the α-cefazolin sodium. Marginal differences observed among CEZ-Na pentahydrate 1, 2, and 3 were speculated as the proportion of conformation 2. Understanding the differences in the polymorphic structure of α-cefazolin sodium may help with making modifications to incorporate new knowledge with a product’s development.

Hydrothermal synthesis for new multifunctional materials: A few examples of phosphates and phosphonate-based hybrid materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rueff, Jean-Michel, E-mail: jean-michel.rueff@ensicaen.fr; Poienar, Maria; Guesdon, Anne

Novel physical or chemical properties are expected in a great variety of materials, in connection with the dimensionality of their structures and/or with their nanostructures, hierarchical superstructures etc. In the search of new advanced materials, the hydrothermal technique plays a crucial role, mimicking the nature able to produce fractal, hyperbranched, urchin-like or snow flake structures. In this short review including new results, this will be illustrated by examples selected in two types of materials, phosphates and phosphonates, prepared by this method. The importance of the synthesis parameters will be highlighted for a magnetic iron based phosphates and for hybrids containingmore » phosphonates organic building units crystallizing in different structural types. - Graphical abstract: Phosphate dendrite like and phosphonate platelet crystals.« less

Exploiting MIC architectures for the simulation of channeling of charged particles in crystals

NASA Astrophysics Data System (ADS)

Bagli, Enrico; Karpusenko, Vadim

2016-08-01

Coherent effects of ultra-relativistic particles in crystals is an area of science under development. DYNECHARM + + is a toolkit for the simulation of coherent interactions between high-energy charged particles and complex crystal structures. The particle trajectory in a crystal is computed through numerical integration of the equation of motion. The code was revised and improved in order to exploit parallelization on multi-cores and vectorization of single instructions on multiple data. An Intel Xeon Phi card was adopted for the performance measurements. The computation time was proved to scale linearly as a function of the number of physical and virtual cores. By enabling the auto-vectorization flag of the compiler a three time speedup was obtained. The performances of the card were compared to the Dual Xeon ones.

Cylindrically symmetric Green's function approach for modeling the crystal growth morphology of ice.

PubMed

Libbrecht, K G

1999-08-01

We describe a front-tracking Green's function approach to modeling cylindrically symmetric crystal growth. This method is simple to implement, and with little computer power can adequately model a wide range of physical situations. We apply the method to modeling the hexagonal prism growth of ice crystals, which is governed primarily by diffusion along with anisotropic surface kinetic processes. From ice crystal growth observations in air, we derive measurements of the kinetic growth coefficients for the basal and prism faces as a function of temperature, for supersaturations near the water saturation level. These measurements are interpreted in the context of a model for the nucleation and growth of ice, in which the growth dynamics are dominated by the structure of a disordered layer on the ice surfaces.

Description of the atomic disorder (local order) in crystals by the mixed-symmetry method

NASA Astrophysics Data System (ADS)

Dudka, A. P.; Novikova, N. E.

2017-11-01

An approach to the description of local atomic disorder (short-range order) in single crystals by the mixed-symmetry method based on Bragg scattering data is proposed, and the corresponding software is developed. In defect-containing crystals, each atom in the unit cell can be described by its own symmetry space group. The expression for the calculated structural factor includes summation over different sets of symmetry operations for different atoms. To facilitate the search for new symmetry elements, an "atomic disorder expert" was developed, which estimates the significance of tested models. It is shown that the symmetry lowering for some atoms correlates with the existence of phase transitions (in langasite family crystals) and the anisotropy of physical properties (in rare-earth dodecaborides RB12).

Tin induced a-Si crystallization in thin films of Si-Sn alloys

NASA Astrophysics Data System (ADS)

Neimash, V.; Poroshin, V.; Shepeliavyi, P.; Yukhymchuk, V.; Melnyk, V.; Kuzmich, A.; Makara, V.; Goushcha, A. O.

2013-12-01

Effects of tin doping on crystallization of amorphous silicon were studied using Raman scattering, Auger spectroscopy, scanning electron microscopy, and X-ray fluorescence techniques. Formation of silicon nanocrystals (2-4 nm in size) in the amorphous matrix of Si1-xSnx, obtained by physical vapor deposition of the components in vacuum, was observed at temperatures around 300 °C. The aggregate volume of nanocrystals in the deposited film of Si1-xSnx exceeded 60% of the total film volume and correlated well with the tin content. Formation of structures with ˜80% partial volume of the nanocrystalline phase was also demonstrated. Tin-induced crystallization of amorphous silicon occurred only around the clusters of metallic tin, which suggested the crystallization mechanism involving an interfacial molten Si:Sn layer.

3D light harnessing based on coupling engineering between 1D-2D Photonic Crystal membranes and metallic nano-antenna.

PubMed

Belarouci, Ali; Benyattou, Taha; Letartre, Xavier; Viktorovitch, Pierre

2010-09-13

A new approach is proposed for the optimum addressing of a metallic nano-antenna (NA) with a free space optical beam. This approach relies on the use of an intermediate resonator structure that provides the appropriate modal conversion of the incoming beam. More precisely, the intermediate resonator consists in a Photonic Crystal (PC) membrane resonant structure that takes benefit of surface addressable slow Bloch modes. First, a phenomenological approach including a deep physical understanding of the NA-PC coupling and its optimization is presented. In a second step, the main features of this analysis are confirmed by numerical simulations (FDTD).

Theoretical Calculations of Refractive Properties for Hg3Te2Cl2 Crystals

NASA Astrophysics Data System (ADS)

Bokotey, O. V.

2016-05-01

This paper reviews the optical properties, such as refractive index, optical dielectric constant, and reflection coefficient of the Hg3Te2Cl2 crystals. The applications of the Hg3X2Y2 crystals as electronic, optical, and optoelectronic devices are very much determined by the nature and magnitude of these fundamental material properties. The origin of chemical bonding in the crystals is very important for definition of the physical and chemical properties. The main structural feature of the Hg3X2Y2 crystals is the presence of covalent pyramids [XHg3] and linear X-Hg-X groups. Optical properties are calculated according to the model proposed by Harrison. The refractive index in the spectral region far from the absorption edge is determined within the generalized single-oscillator model. The calculated results are found to be in good agreement with experimental data.

Crystalline Structure and Physical Properties of UCo2Al3

NASA Astrophysics Data System (ADS)

Verdín, E.; Escudero, R.

Some intermetallic compounds which contain uranium or cerium present heavy fermion characteristics. Take, for example, in the UM2Al3 (M=Pd, Ni) family, superconductivity and magnetism coexist and present heavy fermion behavior. This work presents the crystallographic characteristics and physical properties of a new compound of this family; the intermetallic compound UCo2Al3. Our initial crystallographic studies performed in a small single crystal show that the structure is hexagonal and similar to the UNi2Al3 and UPd2Al3 parent compounds. The space group is P6/mmm with a=5.125 Å and c=4.167 Å crystalline parameters. Measurements of resistivity and magnetization performed on the single crystal reveal that the compound is not superconducting when measured at about 1.8 K. The compound is highly anisotropic and features related to Kondo-like behavior are observed. A weak ferromagnetic transition is observed at a temperature of about 20 K.

Supramolecular Polymer Network-Mediated Self-Assembly of Semicrystalline Polymers with Excellent Crystalline Performance.

PubMed

Cheng, Chih-Chia; Chuang, Wei-Tsung; Lee, Duu-Jong; Xin, Zhong; Chiu, Chih-Wei

2017-03-01

A novel application of supramolecular interactions within semicrystalline polymers, capable of self-assembling into supramolecular polymer networks via self-complementary multiple hydrogen-bonded complexes, is demonstrated for efficient construction of highly controlled self-organizing hierarchical structures to offer a direct, efficient nucleation pathway resulting in superior crystallization performance. Herein, a novel functionalized poly(ε-caprolactone) containing self-complementary sextuple hydrogen-bonded uracil-diamidopyridine (U-DPy) moieties is successfully developed and demonstrated excellent thermal and viscoelastic properties as well as high dynamic structural stability in the bulk state due to physical cross-linking created by reversible sextuple hydrogen bonding between U-DPy units. Due to the ability to vary the extent of the reversible network by tuning the U-DPy content, this newly developed material can be readily adjusted to obtain the desired crystalline products with specific characteristics. Importantly, incorporating only 0.1% U-DPy resulted in a polymer with a high crystallization rate constant, short crystallization half-time, and much more rapid crystallization kinetics than pristine PCL, indicating a low content of U-DPy moieties provides highly efficient nucleation sites that manipulate the nucleation and growth processes of polymer crystals to promote crystallization and chain alignment in bulk. This new system is suggested as a potential new route to substantially improve the performance of polymer crystallization. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elemental and cooperative diffusion in a liquid, supercooled liquid and glass resolved

NASA Astrophysics Data System (ADS)

Cassar, Daniel R.; Lancelotti, Ricardo F.; Nuernberg, Rafael; Nascimento, Marcio L. F.; Rodrigues, Alisson M.; Diz, Luiza T.; Zanotto, Edgar D.

2017-07-01

The diffusion mechanisms controlling viscous flow, structural relaxation, liquid-liquid phase separation, crystal nucleation, and crystal growth in multicomponent glass-forming liquids are of great interest and relevance in physics, chemistry, materials, and glass science. However, the diffusing entities that control each of these important dynamic processes are still unknown. The main objective of this work is to shed some light on this mystery, advancing the knowledge on this phenomenon. For that matter, we measured the crystal growth rates, the viscosity, and lead diffusivities in PbSiO3 liquid and glass in a wide temperature range. We compared our measured values with published data covering 16 orders of magnitude. We suggest that above a certain temperature range Td (1.2Tg-1.3Tg), crystal growth and viscous flow are controlled by the diffusion of silicon and lead. Below this temperature, crystal growth and viscous flow are more sluggish than the diffusion of silicon and lead. Therefore, Td marks the temperature where decoupling between the (measured) cationic diffusivity and the effective diffusivities calculated from viscosity and crystal growth rates occurs. We reasonably propose that the nature or size of the diffusional entities controlling viscous flow and crystal growth below Td is quite different; the slowest is the one controlling viscous flow, but both processes require cooperative movements of some larger structural units rather than jumps of only one or a few isolated atoms.

Investigation on synthesis, growth, structure and physical properties of AgGa0.5In0.5S2 single crystals for Mid-IR application

NASA Astrophysics Data System (ADS)

Karunagaran, N.; Ramasamy, P.

2018-02-01

Silver Gallium Indium Sulfide (AgGa0.5In0.5S2) belongs to the family of AIBIIIC2VI ternary compound semiconductors which crystallize in the chalcopyrite structure. Synthesis of the polycrystalline material from the starting elements is achieved using melt temperature oscillation method. The AgGa0.5In0.5S2 single crystals have been grown by the vertical Bridgman technique. The synthesized AgGa0.5In0.5S2 polycrystalline charge was confirmed by powder XRD. The peak positions are in good agreement with the powder diffraction file. Thermal property was analyzed using differential scanning calorimetry (DSC) technique. The melting point of the crystal is 896 °C and freezing point is 862 °C. The unit cell parameters were confirmed by single crystal X-ray. The transmittance of the grown crystal is 55% in the NIR region and 60% in the mid-IR region. The optical band gap was found to be 2.0 eV. The stoichiometric composition of AgGa0.5In0.5S2 was measured using energy dispersive spectrometry (EDS). The photoluminescence behavior of AgGa0.5In0.5S2 has been analyzed. The resistivity of the grown single crystal has been measured.

Co-crystal formation between two organic solids on the surface of Titan

NASA Astrophysics Data System (ADS)

Cable, M. L.; Vu, T. H.; Maynard-Casely, H. E.; Hodyss, R. P.

2017-12-01

Laboratory experiments of Titan molecular materials, informed by modeling, can help us to understand the complex and dynamic surface processes occurring on this moon at cryogenic temperatures. We previously demonstrated that two common organic materials on Titan, ethane and benzene, form a unique and stable co-crystalline structure at Titan surface temperatures. We have now characterized a second co-crystal that is stable on Titan, this time between two solids: acetylene and ammonia. The co-crystal forms within minutes at Titan surface temperature, as evidenced by new Raman spectral features in the lattice vibration and C-H bending regions. In addition, a red shift of the C-H stretching mode suggests that the acetylene-ammonia co-crystal is stabilized by a network of C-H···N interactions. Thermal stability studies indicate that this co-crystal remains intact to >110 K, and experiments with liquid methane and ethane reveal the co-crystal to be resistant to fluvial or pluvial exposure. Non-covalently bound structures such as these co-crystals point to far more complex surface interactions than previously believed on Titan. New physical and mechanical properties (deformation, plasticity, density, etc.), differences in storage of key species (i.e., ethane versus methane), variations in surface transport and new chemical gradients can all result in diverse surface features and chemistries of astrobiological interest.

An Apparatus for Growth of Small Crystals From Solutions.

ERIC Educational Resources Information Center

Mitrovic, Mico M.

1995-01-01

Describes an apparatus for crystal growth that was designed to study growth kinetics of small crystals from solutions and to obtain crystals of various substances. Describes the use of the apparatus in laboratory practical experiments in the field of crystal growth physics within the course "Solid State Physics". (JRH)

Crystal structure, stability and spectroscopic properties of methane and CO2 hydrates.

PubMed

Martos-Villa, Ruben; Francisco-Márquez, Misaela; Mata, M Pilar; Sainz-Díaz, C Ignacio

2013-07-01

Methane hydrates are highly present in sea-floors and in other planets and their moons. Hence, these compounds are of great interest for environment, global climate change, energy resources, and Cosmochemistry. The knowledge of stability and physical-chemical properties of methane hydrate crystal structure is important for evaluating some new green becoming technologies such as, strategies to produce natural gas from marine methane hydrates and simultaneously store CO2 as hydrates. However, some aspects related with their stability, spectroscopic and other chemical-physical properties of both hydrates are not well understood yet. The structure and stability of crystal structure of methane and CO2 hydrates have been investigated by means of calculations with empirical interatomic potentials and quantum-mechanical methods based on Hartree-Fock and Density Functional Theory (DFT) approximations. Molecular Dynamic simulations have been also performed exploring different configurations reproducing the experimental crystallographic properties. Spectroscopic properties have also been studied. Frequency shifts of the main vibration modes were observed upon the formation of these hydrates, confirming that vibration stretching peaks of C-H at 2915cm(-1) and 2905cm(-1) are due to methane in small and large cages, respectively. Similar effect is observed in the CO2 clathrates. The guest-host binding energy in these clathrates calculated with different methods are compared and discussed in terms of adequacy of empirical potentials and DFT methods for describing the interactions between gas guest and the host water cage, proving an exothermic nature of methane and CO2 hydrates formation process. Copyright © 2013 Elsevier Inc. All rights reserved.

Swinging Symmetry, Multiple Structural Phase Transitions, and Versatile Physical Properties in RECuGa3 (RE = La-Nd, Sm-Gd).

PubMed

Subbarao, Udumula; Rayaprol, Sudhindra; Dally, Rebecca; Graf, Michael J; Peter, Sebastian C

2016-01-19

The compounds RECuGa3 (RE = La-Nd, Sm-Gd) were synthesized by various techniques. Preliminary X-ray diffraction (XRD) analyses at room temperature suggested that the compounds crystallize in the tetragonal system with either the centrosymmetric space group I4/mmm (BaAl4 type) or the non-centrosymmetric space group I4mm (BaNiSn3 type). Detailed single-crystal XRD, neutron diffraction, and synchrotron XRD studies of selected compounds confirmed the non-centrosymmetric BaNiSn3 structure type at room temperature with space group I4mm. Temperature-dependent single-crystal XRD, powder XRD, and synchrotron beamline measurements showed a structural transition between centro- and non-centrosymmetry followed by a phase transition to the Rb5Hg19 type (space group I4/m) above 400 K and another transition to the Cu3Au structure type (space group Pm3̅m) above 700 K. Combined single-crystal and synchrotron powder XRD studies of PrCuGa3 at high temperatures revealed structural transitions at higher temperatures, highlighting the closeness of the BaNiSn3 structure to other structure types not known to the RECuGa3 family. The crystal structure of RECuGa3 is composed of eight capped hexagonal prism cages [RE4Cu4Ga12] occupying one rare-earth atom in each ring, which are shared through the edge of Cu and Ga atoms along the ab plane, resulting in a three-dimensional network. Resistivity and magnetization measurements demonstrated that all of these compounds undergo magnetic ordering at temperatures between 1.8 and 80 K, apart from the Pr and La compounds: the former remains paramagnetic down to 0.3 K, while superconductivity was observed in the La compound at T = 1 K. It is not clear whether this is intrinsic or due to filamentary Ga present in the sample. The divalent nature of Eu in EuCuGa3 was confirmed by magnetization measurements and X-ray absorption near edge spectroscopy and is further supported by the crystal structure analysis.

Optical properties of periodic, quasi-periodic, and disordered one-dimensional photonic structures

NASA Astrophysics Data System (ADS)

Bellingeri, Michele; Chiasera, Alessandro; Kriegel, Ilka; Scotognella, Francesco

2017-10-01

Photonic structures are building blocks for many optical applications in which light manipulation is required spanning optical filtering, lasing, light emitting diodes, sensing and photovoltaics. The fabrication of one-dimensional photonic structures is achievable with a variety of different techniques, such as spin coating, sputtering, evaporation, pulse laser deposition, or extrusion. Such different techniques enable facile integration of the photonic structure with many types of devices. Photonic crystals are characterized by a spatial modulation of the dielectric constant on the length scale of the wavelength of light giving rise to energy ranges where light cannot propagate through the crystal - the photonic band gap. While mostly photonic crystals are referred to as periodic arrangements, in this review we aim to highlight as well how aperiodicity and disorder affects light modulation. In this review article, we introduce the concepts of periodicity, quasi-periodicity, and disorder in photonic crystals, focussing on the one-dimensional case. We discuss in detail the physical peculiarities, the fabrication techniques, and the applications of periodic, quasi-periodic, and disorder photonic structures, highlighting how the degree of crystallinity matters in the manipulation of light. We report different types of disorder in 1D photonic structures and we discuss their properties in terms of light transmission. We discuss the relationship between the average total transmission, in a range of wavelengths around the photonic band gap of the corresponding photonic crystal, and the homogeneity of the photonic structures, quantified by the Shannon index. Then we discuss the light transmission in structures in which the high refractive index layers are aggregated in clusters following a power law distribution. Finally, in the case of structures in which the high refractive index layers are aggregated in clusters with a truncated uniform distribution, we discuss: i) how different refractive index contrast tailors the total light transmission; ii) how the total light transmission is affected by the introduction of defects made with a third material.

Superconducting selenides intercalated with organic molecules: synthesis, crystal structure, electric and magnetic properties, superconducting properties, and phase separation in iron based-chalcogenides and hybrid organic-inorganic superconductors

NASA Astrophysics Data System (ADS)

Krzton-Maziopa, Anna; Pesko, Edyta; Puzniak, Roman

2018-06-01

Layered iron-based superconducting chalcogenides intercalated with molecular species are the subject of intensive studies, especially in the field of solid state chemistry and condensed matter physics, because of their intriguing chemistry and tunable electric and magnetic properties. Considerable progress in the research, revealing superconducting inorganic–organic hybrid materials with transition temperatures to superconducting state, T c, up to 46 K, has been brought in recent years. These novel materials are synthesized by low-temperature intercalation of molecular species, such as solvates of alkali metals and nitrogen-containing donor compounds, into layered FeSe-type structure. Both the chemical nature as well as orientation of organic molecules between the layers of inorganic host, play an important role in structural modifications and may be used for fine tuning of superconducting properties. Furthermore, a variety of donor species compatible with alkali metals, as well as the possibility of doping also in the host structure (either on Fe or Se sites), makes this system quite flexible and gives a vast array of new materials with tunable electric and magnetic properties. In this review, the main aspects of intercalation chemistry are discussed with a particular attention paid to the influence of the unique nature of intercalating species on the crystal structure and physical properties of the hybrid inorganic–organic materials. To get a full picture of these materials, a comprehensive description of the most effective chemical and electrochemical methods, utilized for synthesis of intercalated species, with critical evaluation of their strong and weak points, related to feasibility of synthesis, phase purity, crystal size and morphology of final products, is included as well.

Diversity of Knot Solitons in Liquid Crystals Manifested by Linking of Preimages in Torons and Hopfions

NASA Astrophysics Data System (ADS)

Ackerman, Paul J.; Smalyukh, Ivan I.

2017-01-01

Topological solitons are knots in continuous physical fields classified by nonzero Hopf index values. Despite arising in theories that span many branches of physics, from elementary particles to condensed matter and cosmology, they remain experimentally elusive and poorly understood. We introduce a method of experimental and numerical analysis of such localized structures in liquid crystals that, similar to the mathematical Hopf maps, relates all points of the medium's order parameter space to their closed-loop preimages within the three-dimensional solitons. We uncover a surprisingly large diversity of naturally occurring and laser-generated topologically nontrivial solitons with differently knotted nematic fields, which previously have not been realized in theories and experiments alike. We discuss the implications of the liquid crystal's nonpolar nature on the knot soliton topology and how the medium's chirality, confinement, and elastic anisotropy help to overcome the constraints of the Hobart-Derrick theorem, yielding static three-dimensional solitons without or with additional defects. Our findings will establish chiral nematics as a model system for experimental exploration of topological solitons and may impinge on understanding of such nonsingular field configurations in other branches of physics, as well as may lead to technological applications.

Massive cellular disruption occurs during early imbibition of Cuphea seeds containing crystallized triacylglycerols.

PubMed

Volk, Gayle M; Crane, Jennifer; Caspersen, Ann M; Hill, Lisa M; Gardner, Candice; Walters, Christina

2006-11-01

The transition from anhydrobiotic to hydrated state occurs during early imbibition of seeds and is lethal if lipid reserves in seeds are crystalline. Low temperatures crystallize lipids during seed storage. We examine the nature of cellular damage observed in seeds of Cuphea wrightii and C. lanceolata that differ in triacylglycerol composition and phase behavior. Intracellular structure, observed using transmission electron microscopy, is profoundly and irreversibly perturbed if seeds with crystalline triacylglycerols are imbibed briefly. A brief heat treatment that melts triacylglycerols before imbibition prevents the loss of cell integrity; however, residual effects of cold treatments in C. wrightii cells are reflected by the apparent coalescence of protein and oil bodies. The timing and temperature dependence of cellular changes suggest that damage arises via a physical mechanism, perhaps as a result of shifts in hydrophobic and hydrophilic interactions when triacylglycerols undergo phase changes. Stabilizers of oil body structure such as oleosins that rely on a balance of physical forces may become ineffective when triacylglycerols crystallize. Recent observations linking poor oil body stability and poor seed storage behavior are potentially explained by the phase behavior of the storage lipids. These findings directly impact the feasibility of preserving genetic resources from some tropical and subtropical species.

Ion Coulomb Crystals and Their Applications

NASA Astrophysics Data System (ADS)

Drewsen, Michael

The following text will give a brief introduction to the physics of the spatially ordered structures, so-called Coulomb crystals, that appear when confined ions are cooled to sufficiently low temperatures. It will as well briefly comment on the very diverse scientific applications of such crystals, which have emerged in the past two decades. While this document lacks figures and many specific references, it is the hope, not the text will stimulate the reader to dig deeper into one or more of the discussed subjects, and inspire her/him to think about new potential applications. A fully referenced journal article of essentially the same text can be found in Physica B 460, 105 (2015) [1].

Photonic crystal slab waveguides in moderate index contrast media: Generalized transverse Bragg waveguides

NASA Astrophysics Data System (ADS)

Burckel, David Bruce

One of the anticipated advantages of photonic crystal waveguides is the ability to tune waveguide dispersion and propagation characteristics to achieve desired properties. The majority of research into photonic crystal waveguides centers around high index contrast photonic crystal waveguides with complete in-plane bandgaps in the photonic crystal cladding. This work focuses on linear photonic crystal waveguides in moderate index materials, with insufficient index contrast to guarantee a complete in-plane bandgap. Using a technique called Interferometric Lithography (IL) as well as standard semiconductor processing steps, a process flow for creating large area (˜cm 2), linear photonic crystal waveguides in a spin-deposited photocurable polymer is outlined. The study of such low index contrast photonic crystal waveguides offers a unique opportunity to explore the mechanisms governing waveguide confinement and photonic crystal behavior in general. Results from two optical characterization experiments are provided. In the first set of experiments, rhodamine 590 organic laser dye was incorporated into the polymer prior to fabrication of the photonic crystal slab. Emission spectra from waveguide core modes exhibit no obvious spectral selectivity owing to variation in the periodicity or geometry of the photonic crystal. In addition, grating coupled waveguides were fabricated, and a single frequency diode laser was coupled into the waveguide in order to study the transverse mode structure. To this author's knowledge, the optical mode profile images are the first taken of photonic crystal slab waveguides, exhibiting both simple low order mode structure as well as complex high order mode structure inconsistent with effective index theory. However, no obvious correlation between the mode structure and photonic crystal period or geometry was evident. Furthermore, in both the laser dye-doped and grating coupled waveguides, low loss waveguiding was observed regardless of wavelength to period ratio. These optical results indicated a need for a deeper understanding of the confinement/guiding mechanisms in such waveguide structures. A simplification of the full 2-D problem to a more tractable "tilted 1-D" geometry led to the proposal of a new waveguide geometry, Generalized Transverse Bragg Waveguides (GTBW), as well as a new propagation mode characterized by spatial variation in both the transverse direction as well as the direction of propagation. GTBW demonstrate many of the same dispersion tunability traits exhibited in complete bandgap photonic crystal waveguides, under more modest fabrication demands, and moreover provide much insight into photonic crystal waveguide modes of all types. Generalized Transverse Bragg Waveguides are presented in terms of the standard physical properties associated with waveguides, including the dispersion relation, expressions for the spatial field profile, and the concepts of phase and group velocity. In addition, the proposal of at least one obvious application, semiconductor optical amplifiers, is offered.

Theoretical study of local structure for Ni2+ ions at tetragonal sites in K2ZnF4:Ni2+ system.

PubMed

Wang, Su-Juan; Kuang, Xiao-Yu; Lu, Cheng

2008-12-15

A theoretical method for studying the local lattice structure of Ni2+ ions in (NiF6)(4-) coordination complex is presented. Using the ligand-field model, the formulas relating the microscopic spin Hamiltonian parameters with the crystal structure parameters are derived. Based on the theoretical formulas, the 45 x 45 complete energy matrices for d8 (d2) configuration ions in a tetragonal ligand-field are constructed. By diagonalizing the complete energy matrices, the local distortion structure parameters (R perpendicular and R || ) of Ni2+ ions in K2ZnF4:Ni2+ system have been investigated. The theoretical results are accorded well with the experimental values. Moreover, to understand the detailed physical and chemical properties of the fluoroperovskite crystals, the theoretical values of the g factor of K2ZnF4:Ni2+ system at 78 and 290 K are reported first.

Theoretical study of local structure for Ni 2+ ions at tetragonal sites in K 2ZnF 4:Ni 2+ system

NASA Astrophysics Data System (ADS)

Wang, Su-Juan; Kuang, Xiao-Yu; Lu, Cheng

2008-12-01

A theoretical method for studying the local lattice structure of Ni 2+ ions in (NiF 6) 4- coordination complex is presented. Using the ligand-field model, the formulas relating the microscopic spin Hamiltonian parameters with the crystal structure parameters are derived. Based on the theoretical formulas, the 45 × 45 complete energy matrices for d8 ( d2) configuration ions in a tetragonal ligand-field are constructed. By diagonalizing the complete energy matrices, the local distortion structure parameters ( R⊥ and R||) of Ni 2+ ions in K 2ZnF 4:Ni 2+ system have been investigated. The theoretical results are accorded well with the experimental values. Moreover, to understand the detailed physical and chemical properties of the fluoroperovskite crystals, the theoretical values of the g factor of K 2ZnF 4:Ni 2+ system at 78 and 290 K are reported first.

Preparing highly ordered glasses of discotic liquid crystalline systems by vapor deposition

NASA Astrophysics Data System (ADS)

Gujral, Ankit; Gomez, Jaritza; Bishop, Camille E.; Toney, Michael F.; Ediger, M. D.

Anisotropic molecular packing, particularly in highly ordered liquid-crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized out-of-equilibrium (glassy) solids of discotic liquid-crystalline (LC) systems. Using grazing incidence x-ray scattering, we compare 3 systems: a rectangular columnar LC, a hexagonal columnar LC and a non-liquid crystal former. The packing motifs accessible by vapor deposition are highly organized and vary from face-on to edge-on columnar arrangements depending upon substrate temperature. A subset of these structures cannot be accessed under equilibrium conditions. The structures formed at a given substrate temperature can be understood as the result of the system partially equilibrating toward the structure of the free surface of the equilibrium liquid crystal. Consistent with this view, the structures formed are independent of the substrate material.

Assembly of the most topologically regular two-dimensional micro and nanocrystals with spherical, conical, and tubular shapes

NASA Astrophysics Data System (ADS)

Roshal, D. S.; Konevtsova, O. V.; Myasnikova, A. E.; Rochal, S. B.

2016-11-01

We consider how to control the extension of curvature-induced defects in the hexagonal order covering different curved surfaces. In these frames we propose a physical mechanism for improving structures of two-dimensional spherical colloidal crystals (SCCs). For any SCC comprising of about 300 or less particles the mechanism transforms all extended topological defects (ETDs) in the hexagonal order into the point disclinations. Perfecting the structure is carried out by successive cycles of the particle implantation and subsequent relaxation of the crystal. The mechanism is potentially suitable for obtaining colloidosomes with better selective permeability. Our approach enables modeling the most topologically regular tubular and conical two-dimensional nanocrystals including various possible polymorphic forms of the HIV viral capsid. Different HIV-like shells with an arbitrary number of structural units (SUs) and desired geometrical parameters are easily formed. Faceting of the obtained structures is performed by minimizing the suggested elastic energy.

Synthesis, crystal structure and electrical properties of the tetrahedral quaternary chalcogenides CuM{sub 2}InTe{sub 4} (M=Zn, Cd)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nolas, George S., E-mail: gnolas@usf.edu; Hassan, M. Shafiq; Dong, Yongkwan

Quaternary chalcogenides form a large class of materials that continue to be of interest for energy-related applications. Certain compositions have recently been identified as possessing good thermoelectric properties however these materials typically have the kesterite structure type with limited variation in composition. In this study we report on the structural, optical and electrical properties of the quaternary chalcogenides CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} which crystallize in the modified zinc-blende crystal structure, and compare their properties with that of CuZn{sub 2}InSe{sub 4}. These p-type semiconductors have direct band gaps of about 1 eV resulting in relatively high Seebeck coefficientmore » and resistivity values. This work expands on the research into quaternary chalcogenides with new compositions and structure types in order to further the fundamental investigation of multinary chalcogenides for potential thermoelectrics applications. - Graphical abstract: The structural, optical and electrical properties of the quaternary chalcogenides CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} are reported for the first time. The unique crystal structure allows for relatively good electrical transports and therefore potential for thermoelectric applications. - Highlights: • The physical properties of CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} are reported for the first time. • These materials have potential for thermoelectric applications. • Their direct band gaps also suggest potential for photovoltaics applications.« less

Structure of the sporulation histidine kinase inhibitor Sda from Bacillus subtilis and insights into its solution state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacques, David A.; Streamer, Margaret; Rowland, Susan L.

2009-06-01

The crystal structure of Sda, a DNA-replication/damage checkpoint inhibitor of sporulation in B. subtilis, has been solved via the MAD method. The subunit arrangement in the crystal has enabled a reappraisal of previous biophysical data, resulting in a new model for the behaviour of the protein in solution. The crystal structure of the DNA-damage checkpoint inhibitor of sporulation, Sda, from Bacillus subtilis, has been solved by the MAD technique using selenomethionine-substituted protein. The structure closely resembles that previously solved by NMR, as well as the structure of a homologue from Geobacillus stearothermophilus solved in complex with the histidine kinase KinB.more » The structure contains three molecules in the asymmetric unit. The unusual trimeric arrangement, which lacks simple internal symmetry, appears to be preserved in solution based on an essentially ideal fit to previously acquired scattering data for Sda in solution. This interpretation contradicts previous findings that Sda was monomeric or dimeric in solution. This study demonstrates the difficulties that can be associated with the characterization of small proteins and the value of combining multiple biophysical techniques. It also emphasizes the importance of understanding the physical principles behind these techniques and therefore their limitations.« less

The crystal structure of human soluble CD14 reveals a bent solenoid with a hydrophobic amino-terminal pocket1

PubMed Central

Kelley, Stacy L.; Lukk, Tiit; Nair, Satish K.; Tapping, Richard I.

2012-01-01

Human monocyte differentiation antigen CD14 is a pattern recognition receptor that enhances innate immune responses to infection by sensitizing host cells to bacterial lipopolysaccharide (LPS; endotoxin), lipoproteins, lipoteichoic acid and other acylated microbial products. CD14 physically delivers these lipidated microbial products to various Toll-like receptor signaling complexes that subsequently induce intracellular proinflammatory signaling cascades upon ligand binding. The ensuing cellular responses are usually protective to the host, but can also result in host fatality through sepsis. In this work, we have determined the X-ray crystal structure of human CD14. The structure reveals a bent solenoid typical of leucine rich repeat proteins with an amino terminal pocket that presumably binds acylated ligands including LPS. Comparison of human and mouse CD14 structures show great similarity in overall protein fold. However, compared to mouse CD14, human CD14 contains an expanded pocket and alternative rim residues that are likely to be important for LPS binding and cell activation. The X-ray crystal structure of human CD14 presented herein may foster additional ligand bound structural studies, virtual docking studies, and drug design efforts to mitigate LPS induced sepsis and other inflammatory diseases. PMID:23264655

Growth of urea crystals by physical vapor transport

NASA Technical Reports Server (NTRS)

Feigelson, R. S.; Route, R. K.; Kao, T.-M.

1985-01-01

This work demonstrates that high optical quality crystals of urea can be grown by the physical vapor transport method. The unique features of this method are compared with growth from methanol/water solutions. High growth rates, exceeding 2.5 mm/day, were achieved, and cm-size optical quality single crystals were obtained. Details of the growth technique and the physical properties of the crystals are presented.

The Tunneling Microscope: A New Look at the Atomic World.

ERIC Educational Resources Information Center

Golovchenko, J. A.

1986-01-01

A new instrument called the tunneling microscope has recently been developed that is capable of generating real-space images of surfaces showing atomic structure. Discusses current capabilities, limitations, and the physics involved in the technique. Includes results from a study of silicon crystal surfaces. (JN)

The Chemical Bond and Solid-state Physics

ERIC Educational Resources Information Center

Phillips, James C.

1970-01-01

Proposes a new scale of ionicity, with which the ionic character of bonding in crystals can be predicted and measured. This new scale of ionicity has led to improved understanding of such crystalline properties as lattice structure, heats of formation, elastic constants, and nonlinear optical properties. Bibliography. (LC)

Thermal crystallization mechanism of silk fibroin protein

NASA Astrophysics Data System (ADS)

Hu, Xiao

In this thesis, the thermal crystallization mechanism of silk fibroin protein from Bombyx mori silkworm, was treated as a model for the general study of protein based materials, combining theories from both biophysics and polymer physics fields. A systematic and scientific path way to model the dynamic beta-sheet crystallization process of silk fibroin protein was presented in the following sequence: (1) The crystallinity, fractions of secondary structures, and phase compositions in silk fibroin proteins at any transition stage were determined. Two experimental methods, Fourier transform infrared spectroscopy (FTIR) with Fourier self-deconvolution, and specific reversing heat capacity, were used together for the first time for modeling the static structures and phases in the silk fibroin proteins. The protein secondary structure fractions during the crystallization were quantitatively determined. The possibility of existence of a "rigid amorphous phase" in silk protein was also discussed. (2) The function of bound water during the crystallization process of silk fibroin was studied using heat capacity, and used to build a silk-water dynamic crystallization model. The fundamental concepts and thermal properties of silk fibroin with/without bound water were discussed. Results show that intermolecular bound water molecules, acting as a plasticizer, will cause silk to display a water-induced glass transition around 80°C. During heating, water is lost, and the change of the microenvironment in the silk fibroin chains induces a mesophase prior to thermal crystallization. Real time FTIR during heating and isothermal holding above Tg show the tyrosine side chain changes only during the former process, while beta sheet crystallization occurs only during the latter process. Analogy is made between the crystallization of synthetic polymers according to the four-state scheme of Strobl, and the crystallization process of silk fibroin, which includes an intermediate precursor stage before crystallization. (3) The beta-sheet crystallization kinetics in silk fibroin protein were measured using X-ray, FTIR and heat flow, and the structure reveals the formation mechanism of the silk crystal network. Avrami kinetics theories, which were established for studies of synthetic polymer crystal growth, were for the first time extended to investigate protein self-assembly in multiblock silk fibroin samples. The Avrami exponent, n, was close to two for all methods, indicating formation of beta sheet crystals in silk proteins is different from the 3-D spherulitic crystal growth found in most synthetic homopolymers. A microphase separation pattern after chymotrypsin enzyme biodegradation was shown in the protein structures using scanning electron microscopy. A model was then used to explain the crystallization of silk fibroin protein by analogy to block copolymers. (4) The effects of metal ions during the crystallization of silk fibroin was investigated using thermal analysis. Advanced thermal analysis methods were used to analyze the thermal protein-metallic ion interactions in silk fibroin proteins. Results show that K+ and Ca2+ metallic salts play different roles in silk fibroin proteins, which either reduce (K+) or increase (Ca2+ ) the glass transition (Tg) of pure silk protein and affect the thermal stability of this structure.

Effects of physiological environments on the hydration behavior of mineral trioxide aggregate.

PubMed

Lee, Yuan-Ling; Lee, Bor-Shiunn; Lin, Feng-Huei; Yun Lin, Ava; Lan, Wan-Hong; Lin, Chun-Pin

2004-02-01

Utilizing scanning electron microscope, X-ray diffraction (XRD) and microhardness tests, we evaluated how various physiological environments affect the hydration behavior and physical properties of mineral trioxide aggregate (MTA). We found that the microstructure of hydrated MTA consists of cubic and needle-like crystals. The former comprised the principal structure of MTA, whereas the later were less prominent and formed in the inter-grain spaces between the cubic crystals. MTA samples were hydrated in distilled water, normal saline, pH 7, and pH 5. However, no needle-like crystals were observed in the pH 5 specimens, and erosion of the cubic crystal surfaces was noted. XRD indicated a peak corresponding to Portlandite, a hydration product of MTA, and the peak decreased noticeably in the pH 5 group. The pH 5 specimens' microhardness was also significantly weaker compared to the other three groups (p<0.0001). These findings suggest that physiological environmental effects on MTA formation are determined, in part, by environmental pH and the presence of ions. In particular, an acidic environment of pH 5 adversely affects both the physical properties and the hydration behavior of MTA.

Synthesis and Physical Properties of Liquid Crystals: An Interdisciplinary Experiment

ERIC Educational Resources Information Center

Van Hecke, Gerald R.; Karukstis, Kerry K.; Hanhan Li; Hendargo, Hansford C.; Cosand, Andrew J.; Fox, Marja M.

2005-01-01

A study involves multiple chemistry and physics concepts applied to a state of matter that has biological relevance. An experiment involving the synthesis and physical properties of liquid crystals illustrates the interdisciplinary nature of liquid crystal research and the practical devices derived from such research.

Electron microscopy of octacalcium phosphate in the dental calculus.

PubMed

Kakei, Mitsuo; Sakae, Toshiro; Yoshikawa, Masayoshi

2009-12-01

The purpose of this study was to morphologically demonstrate the presence of octacalcium phosphate in the dental calculus by judging from the crystal lattice image and its rapid transformation into apatite crystal, as part of our serial studies on biomineral products. We also aimed to confirm whether the physical properties of octacalcium phosphate are identical with those of the central dark lines observed in crystals of ordinary calcifying hard tissues. Electron micrographs showed that crystals of various sizes form in the dental calculus. The formation of each crystal seemed to be closely associated with the organic substance, possibly originating from degenerated microorganisms at the calcification front. Many crystals had an 8.2-A lattice interval, similar to that of an apatite crystal. Furthermore, some crystals clearly revealed an 18.7-A lattice interval and were vulnerable to electron bombardment. After electron beam exposure, this lattice interval was quickly altered to about half (i.e. 8.2 A), indicating structural conversion. Consequently, a number of apatite crystals in the dental calculus are possibly created by a conversion mechanism involving an octacalcium phosphate intermediate. However, we also concluded that the calcification process in the dental calculus is not similar to that of ordinary calcifying hard tissues.

Intensities and spectral features of the {}^{4}{\\rm{I}}_{13/2}-{}^{4}{\\rm{I}}_{15/2} potential laser transition of Er3+ centers in CaF2-CeF3 disordered crystal

NASA Astrophysics Data System (ADS)

Wang, Qing-Guo; Su, Liangbi; Liu, Jun-Fang; Liu, Bin; Wu, Feng; Luo, Ping; Zhao, Heng-Yu; Shi, Jiao-Jiao; Xue, Yan-Yan; Xu, Xiao-Dong; Ryba-Romanowski, Witold; Solarz, Piotr; Lisiecki, Radoslaw; Wang, Zhan-Shan; Tang, Hui-Li; Xu, Jun

2017-10-01

Not Available Project supported by Shanghai Engineering Research Center for Sapphire Crystals, China (Grant No. 14DZ2252500), the Fund of Key Laboratory of Optoelectronic Materials Chemistry and Physics Chinese Academy of Sciences (Grant No. 2008DP17301), the Fundamental Research Funds for the Central Universities of China, the National Natural Science Foundation of China and China Academy of Engineering Physics Joint Fund (Grant No. U1530152), the National Natural Science Foundation of China (Grant Nos. 61475177 and 61621001), the Natural Science Foundation of Shanghai Municiple, China (Grant No. 13ZR1446100), and the MOE Key Laboratory of Advanced Micro-Structured Materials of China.

Theoretical modeling on the laser-induced phase deformation of liquid crystal optical phased shifter

NASA Astrophysics Data System (ADS)

Zhou, Zhuangqi; Wang, Xiangru; Zhuo, Rusheng; He, Xiaoxian; Wu, Liang; Wang, Xiaolin; Tan, Qinggui; Qiu, Qi

2018-03-01

To improve the working condition of liquid crystal phase shifter on incident laser power, a theoretical model on laser induced phase distortion is built on the physics of heat deposition and heat transfer. Four typical factors (absorption, heat sink structure, cooling fluid rate, and substrate) are analyzed to evaluate the influence of phase distortion when a relative high-power laser is pumped into the liquid crystal phase shifter. Flow rate of cooling fluid and heat sink structure are the most important two factors on improving the limit of incident laser power. Meanwhile, silicon wafer is suggested to replace the back glass contacting the heat sink, because of its higher heat transfer coefficient. If the device is fabricated on the conditions that: the total absorption is 5% and it has a strong heat sink structure with a flow rate of 0.01 m/s, when the incident laser power is 110W, the laser-induced phase deformation on the center is diminished to be less than 0.06, and the maximum temperature increase on the center is less than 1K degree.

Cation-anion interactions and polar structures in the solid state.

PubMed

Marvel, Michael R; Lesage, Julien; Baek, Jaewook; Halasyamani, P Shiv; Stern, Charlotte L; Poeppelmeier, Kenneth R

2007-11-14

Complicated structures where oxygen and fluorine are found together in one framework, where deviations from Pauling's second crystal rule (PSCR) are expected, often result in structures with important physical properties. The [NbOF5]2- anion and therefore all the individual Nb-O and Nb-F bonds are ordered in noncentrosymmetric KNaNbOF5 and centrosymmetric CsNaNbOF5. The Na/K- and Na/Cs-O/F interactions in these phases, in particular the expected deviations from PSCR and the bond valence model, reveal the essential role of the small potassium cations in the acentric packing of the [NbOF5]2- anion. KNaNbOF5 crystallizes in the orthorhombic and polar space group Pna21 (No. 33) with lattice constants a = 11.8653(11) A, b = 5.8826(6) A, c = 8.1258(8) A, and Z = 4, while CsNaNbOF5 crystallizes in the orthorhombic space group Pbcn (No. 60) with lattice constants a = 8.3155(7), b = 13.3176(11), c = 11.1314(9), and Z = 8.

Synthesis, crystal structure and characterization of chiral, three-dimensional anhydrous potassium tris(oxalato)ferrate(III)

NASA Astrophysics Data System (ADS)

Saritha, A.; Raju, B.; Ramachary, M.; Raghavaiah, P.; Hussain, K. A.

2012-11-01

The synthesis, crystal structure and physical properties of chiral, three-dimensional anhydrous potassium tris(oxalato)ferrate(III) [K3Fe(C2O4)3] are described. X-ray analysis reveals that the compound crystallized in the chiral space group P4132 of cubic system with a=b=c=13.5970(2), Z=4. The structure of the complex consists of infinite anionic [Fe(C2O4)3]3- units with distorted octahedral environment of iron surrounded by six oxygen atoms of three oxalato groups. The anionic units are interlinked through K+ ions of three different coordination environments of distorted octahedral, bicapped trigonal prismatic and trigonal prismatic yielding a three-dimensional motif. The two broad absorption bands at 644 and 924 nm from UV-vis-NIR transmittance spectra were ascribed to a ligand-to-metal charge transfer. The room temperature crystalline EPR spectra indicate the high-spin (S=5/2) of Fe(III) ion. The vibrating sample magnetometer measurement shows the paramagnetic nature at room temperature. Thermal studies of the compound confirm the absence of water molecule.

B1 to B2 structural phase transition in LiF under pressure

NASA Astrophysics Data System (ADS)

Jain, Aayushi; Dixit, R. C.

2018-05-01

In the last few decades the alkali halides emerged as crystals with useful applications and their high-pressure behaviour is the most intensively studied subject in high-pressure physics/chemistry, material science, and geosciences. Most alkali halides follow the B1 (NaCl-type)→B2 (CsCl-type) phase-transition route under pressure. In the present paper, we have investigated the characteristics of structural phase transition that occurred in Lithium Florid compound under high pressure. The transition pressure of B1-B2 was calculated using an effective interionic interaction potential (EIOP). The changes of the characteristics of crystals like, Gibbs free energy, cohesive energy, volume collapse, and lattice constant are calculated for the B1 and B2 structures. These data were compared with the available experimental and theoretical data.

Quantum and isotope effects in lithium metal

NASA Astrophysics Data System (ADS)

Ackland, Graeme J.; Dunuwille, Mihindra; Martinez-Canales, Miguel; Loa, Ingo; Zhang, Rong; Sinogeikin, Stanislav; Cai, Weizhao; Deemyad, Shanti

2017-06-01

The crystal structure of elements at zero pressure and temperature is the most fundamental information in condensed matter physics. For decades it has been believed that lithium, the simplest metallic element, has a complicated ground-state crystal structure. Using synchrotron x-ray diffraction in diamond anvil cells and multiscale simulations with density functional theory and molecular dynamics, we show that the previously accepted martensitic ground state is metastable. The actual ground state is face-centered cubic (fcc). We find that isotopes of lithium, under similar thermal paths, exhibit a considerable difference in martensitic transition temperature. Lithium exhibits nuclear quantum mechanical effects, serving as a metallic intermediate between helium, with its quantum effect-dominated structures, and the higher-mass elements. By disentangling the quantum kinetic complexities, we prove that fcc lithium is the ground state, and we synthesize it by decompression.

Influence of bias voltage on structural and optical properties of TiN{sub x} thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Omveer, E-mail: poonia.omveer@gmail.com; Dahiya, Raj P.; Deenbandhu Chhotu Ram University of Science and Technology, Murthal – 131039

In the present work, Ti thin films were deposited on Si substrate using DC sputtering technique. Indigenous hot cathode arc discharge plasma system was used for nitriding over these samples, where the plasma parameters and work piece can be controlled independently. A mixture of H{sub 2} and N{sub 2} gases (in the ratio of 80:20) was supplied into the plasma chamber. The effect of bias voltage on the crystal structure, morphology and optical properties was investigated by employing various physical techniques such as X-ray Diffraction, Atomic Force Microscopy and UV-Vis spectrometry. It was found that bias voltage affects largely themore » crystal structure and band gap which in turn is responsible for the modifications in optical properties of the deposited films.« less

Positioning and joining of organic single-crystalline wires

PubMed Central

Wu, Yuchen; Feng, Jiangang; Jiang, Xiangyu; Zhang, Zhen; Wang, Xuedong; Su, Bin; Jiang, Lei

2015-01-01

Organic single-crystal, one-dimensional materials can effectively carry charges and/or excitons due to their highly ordered molecule packing, minimized defects and eliminated grain boundaries. Controlling the alignment/position of organic single-crystal one-dimensional architectures would allow on-demand photon/electron transport, which is a prerequisite in waveguides and other optoelectronic applications. Here we report a guided physical vapour transport technique to control the growth, alignment and positioning of organic single-crystal wires with the guidance of pillar-structured substrates. Submicrometre-wide, hundreds of micrometres long, highly aligned, organic single-crystal wire arrays are generated. Furthermore, these organic single-crystal wires can be joined within controlled angles by varying the pillar geometries. Owing to the controllable growth of organic single-crystal one-dimensional architectures, we can present proof-of-principle demonstrations utilizing joined wires to allow optical waveguide through small radii of curvature (internal angles of ~90–120°). Our methodology may open a route to control the growth of organic single-crystal one-dimensional materials with potential applications in optoelectronics. PMID:25814032

Crystallization tendencies of modelled Lennard-Jones liquids with different attractions

NASA Astrophysics Data System (ADS)

Valdès, L.-C.; Gerges, J.; Mizuguchi, T.; Affouard, F.

2018-01-01

Molecular dynamics simulations are performed on simple models composed of monoatomic Lennard-Jones atoms for which the repulsive interaction is the same but the attractive part is tuned. We investigate the precise role of the attractive part of the interaction potential on different structural, dynamical, and thermodynamical properties of these systems in the liquid and crystalline states. It includes crystallization trends for which the main physical ingredients involved have been computed: the diffusion coefficient, the Gibbs energy difference between the liquid and the crystalline state, and the crystal-liquid interfacial free energy. Results are compared with predictions from the classical nucleation theory including transient and steady-state regimes at moderate and deeper undercooling. The question of the energetic and entropic impact of the repulsive and attractive part of the interaction potential towards crystallization is also addressed.

Characterisation of calcium phosphate crystals on calcified human aortic vascular smooth muscle cells and potential role of magnesium.

PubMed

Louvet, Loïc; Bazin, Dominique; Büchel, Janine; Steppan, Sonja; Passlick-Deetjen, Jutta; Massy, Ziad A

2015-01-01

Cardiovascular disease including vascular calcification (VC) remains the leading cause of death in patients suffering from chronic kidney disease (CKD). The process of VC seems likely to be a tightly regulated process where vascular smooth muscle cells are playing a key role rather than just a mere passive precipitation of calcium phosphate. Characterisation of the chemical and crystalline structure of VC was mainly led in patients or animal models with CKD. Likewise, Mg2+ was found to be protective in living cells although a potential role for Mg2+ could not be excluded on crystal formation and precipitation. In this study, the crystal formation and the role of Mg2+ were investigated in an in vitro model of primary human aortic vascular smooth muscle cells (HAVSMC) with physical techniques. In HAVSMC incubated with increased Ca x Pi medium, only calcium phosphate apatite crystals (CPA) were detected by Micro-Fourier Transform InfraRed spectroscopy (µFTIR) and Field Effect Scanning Electron Microscope (FE-SEM) and Energy Dispersive X-ray spectrometry (EDX) at the cell layer level. Supplementation with Mg2+ did not alter the crystal composition or structure. The crystal deposition was preferentially positioned near or directly on cells as pictured by FE-SEM observations and EDX measurements. Large µFTIR maps revealed spots of CPA crystals that were associated to the cellular layout. This qualitative analysis suggests a potential beneficial effect of Mg2+ at 5 mM in noticeably reducing the number and intensities of CPA µFTIR spots. For the first time in a model of HAVSMC, induced calcification led to the formation of the sole CPA crystals. Our data seems to exclude a physicochemical role of Mg2+ in altering the CPA crystal growth, composition or structure. Furthermore, Mg2+ beneficial role in attenuating VC should be linked to an active cellular role.

Characterisation of Calcium Phosphate Crystals on Calcified Human Aortic Vascular Smooth Muscle Cells and Potential Role of Magnesium

PubMed Central

Louvet, Loïc; Bazin, Dominique; Büchel, Janine; Steppan, Sonja; Passlick-Deetjen, Jutta; Massy, Ziad A.

2015-01-01

Background Cardiovascular disease including vascular calcification (VC) remains the leading cause of death in patients suffering from chronic kidney disease (CKD). The process of VC seems likely to be a tightly regulated process where vascular smooth muscle cells are playing a key role rather than just a mere passive precipitation of calcium phosphate. Characterisation of the chemical and crystalline structure of VC was mainly led in patients or animal models with CKD. Likewise, Mg2+ was found to be protective in living cells although a potential role for Mg2+ could not be excluded on crystal formation and precipitation. In this study, the crystal formation and the role of Mg2+ were investigated in an in vitro model of primary human aortic vascular smooth muscle cells (HAVSMC) with physical techniques. Methodology/Principal Findings In HAVSMC incubated with increased Ca x Pi medium, only calcium phosphate apatite crystals (CPA) were detected by Micro-Fourier Transform InfraRed spectroscopy (µFTIR) and Field Effect Scanning Electron Microscope (FE — SEM) and Energy Dispersive X-ray spectrometry (EDX) at the cell layer level. Supplementation with Mg2+ did not alter the crystal composition or structure. The crystal deposition was preferentially positioned near or directly on cells as pictured by FE — SEM observations and EDX measurements. Large µFTIR maps revealed spots of CPA crystals that were associated to the cellular layout. This qualitative analysis suggests a potential beneficial effect of Mg2+ at 5 mM in noticeably reducing the number and intensities of CPA µFTIR spots. Conclusions/Significance For the first time in a model of HAVSMC, induced calcification led to the formation of the sole CPA crystals. Our data seems to exclude a physicochemical role of Mg2+ in altering the CPA crystal growth, composition or structure. Furthermore, Mg2+ beneficial role in attenuating VC should be linked to an active cellular role. PMID:25607936

Mapping of spin wave propagation in a one-dimensional magnonic crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ordóñez-Romero, César L., E-mail: cloro@fisica.unam.mx; Lazcano-Ortiz, Zorayda; Aguilar-Huerta, Melisa

2016-07-28

The formation and evolution of spin wave band gaps in the transmission spectrum of a magnonic crystal have been studied. A time and space resolved magneto inductive probing system has been used to map the spin wave propagation and evolution in a geometrically structured yttrium iron garnet film. Experiments have been carried out using (1) a chemically etched magnonic crystal supporting the propagation of magnetostatic surface spin waves, (2) a short microwave pulsed excitation of the spin waves, and (3) direct spin wave detection using a movable magneto inductive probe connected to a synchronized fast oscilloscope. The results show thatmore » the periodic structure not only modifies the spectra of the transmitted spin waves but also influences the distribution of the spin wave energy inside the magnonic crystal as a function of the position and the transmitted frequency. These results comprise an experimental confirmation of Bloch′s theorem in a spin wave system and demonstrate good agreement with theoretical observations in analogue phononic and photonic systems. Theoretical prediction of the structured transmission spectra is achieved using a simple model based on microwave transmission lines theory. Here, a spin wave system illustrates in detail the evolution of a much more general physical concept: the band gap.« less

Glass in Class

ERIC Educational Resources Information Center

Greaves, Neville

2005-01-01

Glass is reviewed from fabrication to application, laying emphasis on the wide-ranging physics involved. This begins with liquids and solids and the way in which glasses are defined and can be demonstrated in the classroom. At the atomic level the regular structure of crystals and their irregular counterparts in glasses are explained through…

Thermoelectric properties of SnSe1-xSx(0

NASA Astrophysics Data System (ADS)

Nguyen, Thi Minh Hai; Duong, Anh Tuan; Duvjir, Ganbat; Trinh, Thi Ly; Nguyen, Van Quang; Kim, Jungdae; Cho, Sunglae

Tin selenide (SnSe), a p-type semiconductor, has attracted many attention due to its excellent thermoelectric efficiency, i.e., ZT = 2.6 along the b-axis of its high temperature phase. This issue has renewed interests in thermoelectric properties of the materials which adopted the same layered structure as SnSe, such as SnS, GeS, and GeSe. Among these compounds, tin (II) sulfide (SnS) is exceptionally attractive because of its natural abundance and low toxicity. However, the experimental results show that SnS has possessed a small value of the figure of merit. To optimize the thermoelectric performance of SnS, making solid solution is a potential way. That is our motivation for the investigation of SnSe1-xSx single crystals' thermoelectric properties. In this study, SnSe1-xSx (0

Metal Flux Growth, Structural Relations, and Physical Properties of EuCu2Ge2 and Eu3T2In9 (T = Cu and Ag).

PubMed

Subbarao, Udumula; Roy, Soumyabrata; Sarma, Saurav Ch; Sarkar, Sumanta; Mishra, Vidyanshu; Khulbe, Yatish; Peter, Sebastian C

2016-10-17

Single crystals (SCs) of the compounds Eu 3 Ag 2 In 9 and EuCu 2 Ge 2 were synthesized through the reactions run in liquid indium. Eu 3 Ag 2 In 9 crystallizes in the La 3 Al 11 structure type [orthorhombic space group (SG) Immm] with the lattice parameters: a = 4.8370(1) Å, b = 10.6078(3) Å, and c = 13.9195(4) Å. EuCu 2 Ge 2 crystallizes in the tetragonal ThCr 2 Si 2 structure type (SG I4/mmm) with the lattice parameters: a = b = 4.2218(1) Å, and c = 10.3394(5) Å. The crystal structure of Eu 3 Ag 2 In 9 is comprised of edge-shared hexagonal rings consisting of indium. The one-dimensional chains of In 6 rings are shared through the edges, which are further interconnected with other six-membered rings forming a three-dimensional (3D) stable crystal structure along the bc plane. The crystal structure of EuCu 2 Ge 2 can be explained as the complex [CuGe] (2+δ)- polyanionic network embedded with Eu ions. These polyanionic networks present in the crystal structure of EuCu 2 Ge 2 are shared through the edges of the 011 plane containing Cu and Ge atoms, resulting in a 3D network. The structural relationship between Eu 3 T 2 In 9 and EuCu 2 Ge 2 has been discussed in detail, and we conclude that Eu 3 T 2 In 9 is the metal deficient variant of EuCu 2 Ge 2 . The magnetic susceptibilities of Eu 3 T 2 In 9 (T = Cu and Ag) and EuCu 2 Ge 2 were measured between 2 and 300 K. In all cases, magnetic susceptibility data followed Curie-Weiss law above 150 K. Magnetic moment values obtained from the measurements indicate the probable mixed/intermediate valent behavior of the europium atoms, which was further confirmed by X-ray absorption studies and bond distances around the Eu atoms. Electrical resistivity measurements suggest that Eu 3 T 2 In 9 and EuCu 2 Ge 2 are metallic in nature.

Characterization of Structural Defects in Wide Band-Gap Compound Materials for Semiconductor and Opto-Electronic Applications

NASA Astrophysics Data System (ADS)

Goue, Ouloide Yannick

Single crystals of binary and ternary compounds are touted to replace silicon for specialized applications in the semiconductor industry. However, the relative high density of structural defects in those crystals has hampered the performance of devices built on them. In order to enhance the performance of those devices, structurally perfect single crystals must be grown. The aim of this thesis is to investigate the interplay between crystal growth process and crystal quality as well as structural defect types and transport property. To this end, the thesis is divided into two parts. The first part provides a general review of the theory of crystal growth (chapter I), an introduction to the materials being investigated (chapter II and III) and the characterization techniques being used (chapter IV). • In chapter I, a brief description of the theory of crystal growth is provided with an eye towards the driving force behind crystal nucleation and growth along with the kinetic factors affecting crystal growth. The case of crystal growth of silicon carbide (SiC) by physical vapor transport (PVT) and chemical vapor deposition (CVD) is discussed. The Bridgman, travelling heater method (THM) and physical transport growth of cadmium zinc telluride (CZT) is also treated. In chapters II and III, we introduce the compound materials being investigated in this study. While a description of their crystal structure and properties is provided, the issues associated with their growth are discussed. In chapter IV, a description of the characterization techniques used in these studies is presented. These techniques are synchrotron X-ray topography (SXRT), transmission electron microscopy, transmission infrared microscopy (TIM), micro-Raman spectroscopy (muRS) and light microscopy. Extensive treatment of SXRT technique is also provided. In the second part, the experimental results obtained in the course of these studies are presented and discussed. These results are divided into three subsections. • The development of a new technique for the production of large and high quality silicon carbide single crystal boule is proposed. This technique herein referred to as Large Tapered Crystal (LTC) growth consists of two steps: growth of long SiC rod crystal by solvent-laser heated floating zone (Solvent-LHFZ) and lateral expansion of a seed by hot wall chemical vapor deposition (HWCVD). Solvent-LHFZ was successful as SiC rod crystals, replicating the polytype structure of the starting seed, were achieved at a growth rate varying from 4 to 100mum/hr. However, SXRT revealed the presence of an inhomogeneous strain in the grown crystal rod. This was further confirmed by SEM images, which showed the platelet-like morphology of the growth front with pockets in which iron (Fe)-rich material from the Fe solvent is trapped. It was furthermore observed that at high Fe to Si ratio (˜1.9), no growth was achieved. HWCVD enlargement was also successful as SiC boules, replicating the polytype structure of the starting seed, were achieved at growth rate of about 180mum/hr. The boules had a faceted hexagonal morphology with a strain-free surface marked by steps. Combination of SXRT, TEM and muRS revealed the presence of stacking disorder in the seed (3C, 4H and 15R-SiC) that replicated in the homoepitaxial layer. The formation of the observed stacking disorder is attributed to the low energy difference between stacking configurations on the growth surface as proposed by Takahashi and Ohtani. • The influence of structural defect type and distribution on minority carrier lifetime in 4H-SiC epilayers was investigated. Structural defect type and distribution map was obtained using SXRT, whereas minority carrier lifetime map was obtained using muPCD. Decrease in carrier lifetime observed from muPCD map was associated with specific structural defects such as low angle grain boundaries (LAGBs), stacking faults (SFs), interfacial dislocations (IDs), half loop arrays (HLAs) as well as basal plane dislocations (BPDs) pinned at TSDs. While the effect of morphological defects was mitigated, combination of defects such as microcracks, overlapping triangular defects and BPD half loops were observed to reduce carrier lifetime. Furthermore, regions of high dislocation density were associated with low carrier lifetime. • Finally, the effect of cadmium (Cd) overpressure on the quality of cadmium zinc telluride crystal ingots was investigated for two set of samples (set 1 and 2). Overall, high resistivity single crystals were achieved. Evaluation of the crystal quality by SXRT revealed that under certain Cd overpressures and growth conditions, the quality of the grown boule improved. Similarly, transmission infrared (IR) microscopy showed a correlation between the size/density and distribution of Te inclusions/precipitates and Cd overpressure. The size of Te inclusions was observed to decrease as a function of Cd overpressure as predicted from partial pressure data for stoichiometric melt. The best improvement in crystalline quality were observed for samples from set 1at a Cd reservoir of 785 °C and for set 2 samples for a Cd reservoir at 825 °C. This difference in Cd reservoir temperature for stoichiometric growth between set 1 and set 2 was attributed to other factors such as rate of cooling of Cd reservoir, rate of cooling of the crystal along with control of the melt interface. The summary of these results and the implication of this growth approach for producing high quality CZT single crystals are discussed.

Free-standing nanomechanical and nanophotonic structures in single-crystal diamond

NASA Astrophysics Data System (ADS)

Burek, Michael John

Realizing complex three-dimensional structures in a range of material systems is critical to a variety of emerging nanotechnologies. This is particularly true of nanomechanical and nanophotonic systems, both relying on free-standing small-scale components. In the case of nanomechanics, necessary mechanical degrees of freedom require physically isolated structures, such as suspended beams, cantilevers, and membranes. For nanophotonics, elements like waveguides and photonic crystal cavities rely on light confinement provided by total internal reflection or distributed Bragg reflection, both of which require refractive index contrast between the device and surrounding medium (often air). Such suspended nanostructures are typically fabricated in a heterolayer structure, comprising of device (top) and sacrificial (middle) layers supported by a substrate (bottom), using standard surface nanomachining techniques. A selective, isotropic etch is then used to remove the sacrificial layer, resulting in free-standing devices. While high-quality, crystalline, thin film heterolayer structures are readily available for silicon (as silicon-on-insulator (SOI)) or III-V semiconductors (i.e. GaAs/AlGaAs), there remains an extensive list of materials with attractive electro-optic, piezoelectric, quantum optical, and other properties for which high quality single-crystal thin film heterolayer structures are not available. These include complex metal oxides like lithium niobate (LiNbO3), silicon-based compounds such as silicon carbide (SiC), III-V nitrides including gallium nitride (GaN), and inert single-crystals such as diamond. Diamond is especially attractive for a variety of nanoscale technologies due to its exceptional physical and chemical properties, including high mechanical hardness, stiffness, and thermal conductivity. Optically, it is transparent over a wide wavelength range (from 220 nm to the far infrared), has a high refractive index (n ~ 2.4), and is host to a vast inventory of luminescent defect centers (many with direct optical access to highly coherent electron and nuclear spins). Diamond has many potential applications ranging from radio frequency nanoelectromechanical systems (RF-NEMS), to all-optical signal processing and quantum optics. Despite the commercial availability of wafer-scale nanocrystalline diamond thin films on foreign substrates (namely SiO2), this diamond-on-insulator (DOI) platform typically exhibits inferior material properties due to friction, scattering, and absorption losses at grain boundaries, significant surface roughness, and large interfacial stresses. In the absence of suitable heteroepitaxial diamond growth, substantial research and development efforts have focused on novel processing techniques to yield nanoscale single-crystal diamond mechanical and optical elements. In this thesis, we demonstrate a scalable 'angled-etching' nanofabrication method for realizing nanomechanical systems and nanophotonic networks starting from bulk single-crystal diamond substrates. Angled-etching employs anisotropic oxygen-based plasma etching at an oblique angle to the substrate surface, resulting in suspended optical structures with triangular cross-sections. Using this approach, we first realize single-crystal diamond nanomechanical resonant structures. These nanoscale diamond resonators exhibit high mechanical quality-factors (approaching Q ~ 105) with mechanical resonances up to 10 MHz. Next, we demonstrate engineered nanophotonic structures, specifically racetrack resonators and photonic crystal cavities, in bulk single-crystal diamond. Our devices feature large optical Q-factors, in excess of 10 5, and operate over a wide wavelength range, spanning visible and telecom. These newly developed high-Q diamond optical nanocavities open the door for a wealth of applications, ranging from nonlinear optics and chemical sensing, to quantum information processing and cavity optomechanics. Beyond isolated nanophotonic devices, we also developed free-standing angled-etched diamond waveguides which efficiently route photons between optical nanocavities, realizing true on-chip diamond nanophotonic networks. A high efficiency fiber-optical interface with aforementioned on-chip diamond nanophotonic networks, achieving > 90% power coupling, is also demonstrated. Lastly, we demonstrate a cavity-optomechanical system in single-crystal diamond, which builds upon previously realized diamond nanobeam photonic crystal cavities fabricated by angled-etching. Specifically, we demonstrate diamond optomechanical crystals (OMCs), where the engineered co-localization of photons and phonons in a quasi-periodic diamond nanostructure leads to coupling of an optical cavity field to a mechanical mode via the radiation pressure of light. In contrast to other material systems, diamond OMCs possess large intracavity photon capacity and sufficient optomechanical coupling rates to exceed a cooperativity of ~ 1 at room temperature and realize large amplitude optomechanical self-oscillations.

Alternative expression of the Bloch wave group velocity in loss-less periodic media using the electromagnetic field energy

NASA Astrophysics Data System (ADS)

Deparis, Olivier; Lambin, Philippe

2018-01-01

In periodic optical media, the group velocity is defined as the gradient with respect to wave-vector of the corresponding Bloch mode frequency dispersion curve, forming the photonic band structure. Instead of deducing it from the numerically computed photonic crystal band structure, the group velocity can be calculated directly from the integral of the Poynting vector over the crystal unit cell, the physical meaning of which is immediately perceivable. The related formula, which can be regarded as the application of Hellmann-Feynman theorem to electromagnetism, has been reported previously though without proof. We provide hereafter a full derivation of that formula starting from Maxwell's equations and we discuss its usefulness in photonics.

Impact of physical and chemical parameters on the hydroxyapatite nanopowder synthesized by chemical precipitation method

NASA Astrophysics Data System (ADS)

Thu Trang Pham, Thi; Phuong Nguyen, Thu; Pham, Thi Nam; Phuong Vu, Thi; Tran, Dai Lam; Thai, Hoang; Thanh Dinh, Thi Mai

2013-09-01

In this paper, the synthesis of hydroxyapatite (HAp) nanopowder was studied by chemical precipitation method at different values of reaction temperature, settling time, Ca/P ratio, calcination temperature, (NH4)2HPO4 addition rate, initial concentration of Ca(NO3)2 and (NH4)2HPO4. Analysis results of properties, morphology, structure of HAp powder from infrared (IR) spectra, x-ray diffraction (XRD), energy dispersive x-ray (EDX) spectra and scanning electron microscopy (SEM) indicated that the synthesized HAp powder had cylinder crystal shape with size less than 100 nm, single-phase structure. The variation of the synthesis conditions did not affect the morphology but affected the size of HAp crystals.

The effect of age on fluid intelligence is fully mediated by physical health.

PubMed

Bergman, Ingvar; Almkvist, Ove

2013-01-01

The present study investigated the extent to which the effect of age on cognitive ability is predicted by individual differences in physical health. The sample consisted of 118 volunteer subjects who were healthy and ranging in age from 26 to 91. The examinations included a clinical investigation, magnetic resonance imaging (MRI) brain neuroimaging, and a comprehensive neuropsychological assessment. The effect of age on fluid IQ with and without visual spatial praxis and on crystallized IQ was tested whether being fully-, partially- or non-mediated by physical health. Structural equation analyses showed that the best and most parsimonious fit to the data was provided by models that were fully mediated for fluid IQ without praxis, non-mediated for crystallized IQ and partially mediated for fluid IQ with praxis. The diseases of the circulatory and nervous systems were the major mediators. It was concluded from the pattern of findings that the effect of age on fluid intelligence is fully mediated by physical health, while crystallized intelligence is non-mediated and visual spatial praxis is partially mediated, influenced mainly by direct effects of age. Our findings imply that improving health by acting against the common age-related circulatory- and nervous system diseases and risk factors will oppose the decline in fluid intelligence with age. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Learning physical descriptors for materials science by compressed sensing

NASA Astrophysics Data System (ADS)

Ghiringhelli, Luca M.; Vybiral, Jan; Ahmetcik, Emre; Ouyang, Runhai; Levchenko, Sergey V.; Draxl, Claudia; Scheffler, Matthias

2017-02-01

The availability of big data in materials science offers new routes for analyzing materials properties and functions and achieving scientific understanding. Finding structure in these data that is not directly visible by standard tools and exploitation of the scientific information requires new and dedicated methodology based on approaches from statistical learning, compressed sensing, and other recent methods from applied mathematics, computer science, statistics, signal processing, and information science. In this paper, we explain and demonstrate a compressed-sensing based methodology for feature selection, specifically for discovering physical descriptors, i.e., physical parameters that describe the material and its properties of interest, and associated equations that explicitly and quantitatively describe those relevant properties. As showcase application and proof of concept, we describe how to build a physical model for the quantitative prediction of the crystal structure of binary compound semiconductors.

On static triplet structures in fluids with quantum behavior.

PubMed

Sesé, Luis M

2018-03-14

The problem of the equilibrium triplet structures in fluids with quantum behavior is discussed. Theoretical questions of interest to the real space structures are addressed by studying the three types of structures that can be determined via path integrals (instantaneous, centroid, and total thermalized-continuous linear response). The cases of liquid para-H 2 and liquid neon on their crystallization lines are examined with path-integral Monte Carlo simulations, the focus being on the instantaneous and the centroid triplet functions (equilateral and isosceles configurations). To analyze the results further, two standard closures, Kirkwood superposition and Jackson-Feenberg convolution, are utilized. In addition, some pilot calculations with path integrals and closures of the instantaneous triplet structure factor of liquid para-H 2 are also carried out for the equilateral components. Triplet structural regularities connected to the pair radial structures are identified, a remarkable usefulness of the closures employed is observed (e.g., triplet spatial functions for medium-long distances, triplet structure factors for medium k wave numbers), and physical insight into the role of pair correlations near quantum crystallization is gained.

On static triplet structures in fluids with quantum behavior

NASA Astrophysics Data System (ADS)

Sesé, Luis M.

2018-03-01

The problem of the equilibrium triplet structures in fluids with quantum behavior is discussed. Theoretical questions of interest to the real space structures are addressed by studying the three types of structures that can be determined via path integrals (instantaneous, centroid, and total thermalized-continuous linear response). The cases of liquid para-H2 and liquid neon on their crystallization lines are examined with path-integral Monte Carlo simulations, the focus being on the instantaneous and the centroid triplet functions (equilateral and isosceles configurations). To analyze the results further, two standard closures, Kirkwood superposition and Jackson-Feenberg convolution, are utilized. In addition, some pilot calculations with path integrals and closures of the instantaneous triplet structure factor of liquid para-H2 are also carried out for the equilateral components. Triplet structural regularities connected to the pair radial structures are identified, a remarkable usefulness of the closures employed is observed (e.g., triplet spatial functions for medium-long distances, triplet structure factors for medium k wave numbers), and physical insight into the role of pair correlations near quantum crystallization is gained.

The crystal structure of Neisseria gonorrhoeae PriB reveals mechanistic differences among bacterial DNA replication restart pathways

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Jinlan; George, Nicholas P.; Duckett, Katrina L.

2010-05-25

Reactivation of repaired DNA replication forks is essential for complete duplication of bacterial genomes. However, not all bacteria encode homologs of the well-studied Escherichia coli DNA replication restart primosome proteins, suggesting that there might be distinct mechanistic differences among DNA replication restart pathways in diverse bacteria. Since reactivation of repaired DNA replication forks requires coordinated DNA and protein binding by DNA replication restart primosome proteins, we determined the crystal structure of Neisseria gonorrhoeae PriB at 2.7 {angstrom} resolution and investigated its ability to physically interact with DNA and PriA helicase. Comparison of the crystal structures of PriB from N. gonorrhoeaemore » and E. coli reveals a well-conserved homodimeric structure consisting of two oligosaccharide/oligonucleotide-binding (OB) folds. In spite of their overall structural similarity, there is significant species variation in the type and distribution of surface amino acid residues. This correlates with striking differences in the affinity with which each PriB homolog binds single-stranded DNA and PriA helicase. These results provide evidence that mechanisms of DNA replication restart are not identical across diverse species and that these pathways have likely become specialized to meet the needs of individual organisms.« less

Growth, structural, physical and computational perspectives of trans-4-hydroxy-l-proline: a promising organic nonlinear optical material with large laser-induced damage threshold

NASA Astrophysics Data System (ADS)

Thirumurugan, Ramaiah; Anitha, Kandasamy

2017-05-01

In this work, a systematic study of an organic nonlinear optical (NLO) material, trans-4-hydroxy-l-proline (THP), C5H9NO3 is reported. An optical quality single crystals of THP have been successfully grown by using slow evaporation solution growth technique (SEST). The single crystal x-ray diffraction (SXRD) analysis reveals that grown crystal belongs to the orthorhombic system with non-centrosymmetric space group (NCS), P212121. Powder x-ray diffraction (PXRD) analysis shows relatively a good crystalline nature. The molecular structure of THP was recognized by NMR (1H and 13C) studies and its vibrational modes were confirmed by FTIR and FT-Raman vibrational studies. UV-Vis-NIR spectrum of grown crystal shows high optical transparency in the visible and near-IR region with low near-UV cut-off wavelength at 218 nm. Photoluminescence study confirms ultraviolet wavelength emission of THP crystal. The second harmonic generation (SHG) efficiency of grown crystal is 1.6 times greater with respect to standard potassium dihydrogen phosphate (KDP). Nonlinear refractive index (n 2) and nonlinear absorption coefficient (β) were determined using the Z-scan technique. The title compound owns high thermal stability of 294 °C and specific heat capacity (C P) of 1.21 J g-1 K-1 at 300 K and 11.33 J g-1 K-1 at 539 K (melting point). The laser-induced damage threshold (LDT) value of grown crystal was measured as 7.25 GW cm-2. The crystal growth mechanism and defects of grown crystal were studied by chemical etching technique. Mechanical strength was extensively studied by Vickers microhardness test and crystal void percentage analysis. Moreover, density functional theory (DFT) studies were carried out to probe the Mulliken charge distribution, frontier molecular orbitals (FMOs) and first order hyperpolarizability (β) of the optimized molecular structure to get a better insight of the molecular properties. These characterization results endorse that grown THP crystal as a suitable candidate for NLO applications with large LDT.

"Building" 3D visualization skills in mineralogy

NASA Astrophysics Data System (ADS)

Gaudio, S. J.; Ajoku, C. N.; McCarthy, B. S.; Lambart, S.

2016-12-01

Studying mineralogy is fundamental for understanding the composition and physical behavior of natural materials in terrestrial and extraterrestrial environments. However, some students struggle and ultimately get discouraged with mineralogy course material because they lack well-developed spatial visualization skills that are needed to deal with three-dimensional (3D) objects, such as crystal forms or atomic-scale structures, typically represented in two-dimensional (2D) space. Fortunately, spatial visualization can improve with practice. Our presentation demonstrates a set of experiential learning activities designed to support the development and improvement of spatial visualization skills in mineralogy using commercially available magnetic building tiles, rods, and spheres. These instructional support activities guide students in the creation of 3D models that replicate macroscopic crystal forms and atomic-scale structures in a low-pressure learning environment and at low cost. Students physically manipulate square and triangularly shaped magnetic tiles to build 3D open and closed crystal forms (platonic solids, prisms, pyramids and pinacoids). Prismatic shapes with different closing forms are used to demonstrate the relationship between crystal faces and Miller Indices. Silica tetrahedra and octahedra are constructed out of magnetic rods (bonds) and spheres (oxygen atoms) to illustrate polymerization, connectivity, and the consequences for mineral formulae. In another activity, students practice the identification of symmetry elements and plane lattice types by laying magnetic rods and spheres over wallpaper patterns. The spatial visualization skills developed and improved through our experiential learning activities are critical to the study of mineralogy and many other geology sub-disciplines. We will also present pre- and post- activity assessments that are aligned with explicit learning outcomes.

How evolutionary crystal structure prediction works--and why.

PubMed

Oganov, Artem R; Lyakhov, Andriy O; Valle, Mario

2011-03-15

Once the crystal structure of a chemical substance is known, many properties can be predicted reliably and routinely. Therefore if researchers could predict the crystal structure of a material before it is synthesized, they could significantly accelerate the discovery of new materials. In addition, the ability to predict crystal structures at arbitrary conditions of pressure and temperature is invaluable for the study of matter at extreme conditions, where experiments are difficult. Crystal structure prediction (CSP), the problem of finding the most stable arrangement of atoms given only the chemical composition, has long remained a major unsolved scientific problem. Two problems are entangled here: search, the efficient exploration of the multidimensional energy landscape, and ranking, the correct calculation of relative energies. For organic crystals, which contain a few molecules in the unit cell, search can be quite simple as long as a researcher does not need to include many possible isomers or conformations of the molecules; therefore ranking becomes the main challenge. For inorganic crystals, quantum mechanical methods often provide correct relative energies, making search the most critical problem. Recent developments provide useful practical methods for solving the search problem to a considerable extent. One can use simulated annealing, metadynamics, random sampling, basin hopping, minima hopping, and data mining. Genetic algorithms have been applied to crystals since 1995, but with limited success, which necessitated the development of a very different evolutionary algorithm. This Account reviews CSP using one of the major techniques, the hybrid evolutionary algorithm USPEX (Universal Structure Predictor: Evolutionary Xtallography). Using recent developments in the theory of energy landscapes, we unravel the reasons evolutionary techniques work for CSP and point out their limitations. We demonstrate that the energy landscapes of chemical systems have an overall shape and explore their intrinsic dimensionalities. Because of the inverse relationships between order and energy and between the dimensionality and diversity of an ensemble of crystal structures, the chances that a random search will find the ground state decrease exponentially with increasing system size. A well-designed evolutionary algorithm allows for much greater computational efficiency. We illustrate the power of evolutionary CSP through applications that examine matter at high pressure, where new, unexpected phenomena take place. Evolutionary CSP has allowed researchers to make unexpected discoveries such as a transparent phase of sodium, a partially ionic form of boron, complex superconducting forms of calcium, a novel superhard allotrope of carbon, polymeric modifications of nitrogen, and a new class of compounds, perhydrides. These methods have also led to the discovery of novel hydride superconductors including the "impossible" LiH(n) (n=2, 6, 8) compounds, and CaLi(2). We discuss extensions of the method to molecular crystals, systems of variable composition, and the targeted optimization of specific physical properties. © 2011 American Chemical Society

Beating the Heat: Fast Scanning Melts Beta Sheet Crystals

NASA Astrophysics Data System (ADS)

Cebe, Peggy; Hu, Xiao; Kaplan, David; Zhuravlev, Evgeny; Wurm, Andreas; Arbeiter, Daniella; Schick, Christoph

2014-03-01

Beta-pleated-sheet crystals are among the most stable of protein secondary structures, and are responsible for the remarkable physical properties of many fibrous proteins, such as silk. Previous thinking was that beta-pleated-sheet crystals in the dry solid state would not melt upon input of heat energy alone. Indeed, at conventional heating rates (~1-50 °C/min), silk exhibits its glass transition (~175 °C), followed by cold crystallization, and then by immediate thermal degradation beginning at about 225 °C. Here we demonstrate that beta-pleated-sheet crystals can melt directly from the solid state to become random coils, helices, and turns. We use fast scanning chip calorimetry at 2,000 K/s to avoid thermal degradation, and report the first reversible thermal melting of protein beta-pleated-sheet crystals, exemplified by silk fibroin. The similarity between thermal melting behavior of lamellar crystals of synthetic polymers and beta-pleated-sheet crystals is confirmed. The authors acknowledge support from the National Science Foundation and German Academic Exchange Service DAAD; EZ acknowledges a European Union funded Marie Curie EST fellowship (ADVATEC); XH and DK acknowledge NIH P41 Tissue Engineering Resource Center.

Magnetic domains and defects in ferromagnetic liquid crystal colloids realized with optical patterning

NASA Astrophysics Data System (ADS)

Hess, Andrew; Liu, Qingkun; Smalyukh, Ivan

A promising approach in designing composite materials with unusual physical behavior combines solid nanostructures and orientationally ordered soft matter at the mesoscale. Such composites not only inherit properties of their constituents but also can exhibit emergent behavior, such as ferromagnetic ordering of colloidal metal nanoparticles forming mesoscopic magnetization domains when dispersed in a nematic liquid crystal. Here we demonstrate the optical patterning of domain structures and topological defects in such ferromagnetic liquid crystal colloids which allows for altering their response to magnetic fields. Our findings reveal the nature of the defects in this soft matter system which is different as compared to non-polar nematic and ferromagnetic systems alike. This research was supported by the NSF Grant DMR-1420736.

Interaction between Convection and Heat Transfer in Crystal Growth

NASA Technical Reports Server (NTRS)

1998-01-01

Crystals are integral components in some of our most sophisticated and rapidly developing industries. Single crystals are solids with the most uniform structures that can be obtained on an atomic scale. Because of their structural uniformity, crystals can transmit acoustic and electromagnetic waves and charged particles with essentially no scattering or interferences. This transparency, which can be selectively modified by controlled additions of impurities known as dopants, is the foundation of modern electronic industry. It has brought about widespread application of crystals in transistors, lasers, microwave devices, infrared detectors, magnetic memory devices, and many other magnets and electro-optic components. The performance of a crystal depends strongly on its compositional homogeneity. For instance, in modern microcircuitry, compositional variations of a few percent (down to a submicron length scale) can seriously jeopardize predicted yields. Since crystals are grown by carefully controlled phase transformations, the compositional adjustment in the solid is often made during growth from the nutrient. Hence, a detailed understanding of mass transfer in the nutrient is essential. Moreover, since mass transfer is often the slowest process during growth, it is usually the rate limiting mechanism. Crystal growth processes are usually classified according to the nature of the parent phase. Nevertheless, whether the growth occurs by solidification from a melt (melt growth), nucleation from a solution (solution growth), condensation from a vapor (physical vapor transport) or chemical reaction of gases (chemical vapor deposition), the parent phase is a fluid. As is with most non-equilibrium processes involving fluids, liquid or vapor, fluid motion plays an important role, affecting both the concentration and temperature gradients at the soli-liquid interface.

High Surface Area Dendrite Nanoelectrodes for Electrochemistry

NASA Astrophysics Data System (ADS)

Nesbitt, Nathan; Glover, Jennifer; Goyal, Saurabh; Simidjiysky, Svetoslav; Naughton, Michael

2014-03-01

Solution-based electrodeposition of metal using a low ion concentration, surface passivation agents, and/or electrochemical crystal conditioning has allowed for the formation of high surface area metal electrodes, useful for Raman spectroscopy and electrochemical sensors. Additionally, high frequency electrical oscillations have been used to electrically connect co-planar electrodes, a process called directed electrochemical nanowire assembly (DENA). These approaches aim to control the crystal face that metal atoms in solution will nucleate onto, thus causing anisotropic growth of metal crystals. However, DENA has not been used to create high surface area electrodes, and no study has been conducted on the effect of micron-scale surface topography on the initial nucleation of metal crystals on the electrode surface. When DENA is used to create a high surface area electrode, such a texture has a strong impact on the subsequent topography of the three dimensional dendritic structures by limiting the areal density of crystals on the electrode surface. Such structures both demonstrate unique physics concerning the nucleation of metal dendrites, and offer a unique and highly facile fabrication method of high surface area electrodes, useful for chemical and biological sensing. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1258923).

Solution‐crystallization and related phenomena in 9,9‐dialkyl‐fluorene polymers. II. Influence of side‐chain structure

PubMed Central

Perevedentsev, Aleksandr; Stavrinou, Paul N.; Smith, Paul

2015-01-01

ABSTRACT Solution‐crystallization is studied for two polyfluorene polymers possessing different side‐chain structures. Thermal analysis and temperature‐dependent optical spectroscopy are used to clarify the nature of the crystallization process, while X‐ray diffraction and scanning electron microscopy reveal important differences in the resulting microstructures. It is shown that the planar‐zigzag chain conformation termed the β‐phase, which is observed for certain linear‐side‐chain polyfluorenes, is necessary for the formation of so‐called polymer‐solvent compounds for these polymers. Introduction of alternating fluorene repeat units with branched side‐chains prevents formation of the β‐phase conformation and results in non‐solvated, i.e. melt‐crystallization‐type, polymer crystals. Unlike non‐solvated polymer crystals, for which the chain conformation is stabilized by its incorporation into a crystalline lattice, the β‐phase conformation is stabilized by complexation with solvent molecules and, therefore, its formation does not require specific inter‐chain interactions. The presented results clarify the fundamental differences between the β‐phase and other conformational/crystalline forms of polyfluorenes. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 1492–1506 PMID:27546983

Crystal structure and low-energy Einstein mode in ErV{sub 2}Al{sub 20} intermetallic cage compound

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winiarski, Michał J., E-mail: mwiniarski@mif.pg.gda.pl; Klimczuk, Tomasz

Single crystals of a new ternary aluminide ErV{sub 2}Al{sub 20} were grown using a self-flux method. The crystal structure was determined by powder X-ray diffraction measurements and Rietveld refinement, and physical properties were studied by means of electrical resistivity, magnetic susceptibility and specific heat measurements. These measurements reveal that ErV{sub 2}Al{sub 20} is a Curie-Weiss paramagnet down to 1.95 K with an effective magnetic moment μ{sub eff} =9.27(1) μ{sub B} and Curie-Weiss temperature Θ{sub CW} =−0.55(4) K. The heat capacity measurements show a broad anomaly at low temperatures that is attributed to the presence of a low-energy Einstein mode withmore » characteristic temperature Θ{sub E} =44 K, approximately twice as high as in the isostructural ‘Einstein solid’ VAl{sub 10.1}. - Graphical abstract: A low-energy Einstein mode is observed in a novel intermetallic cage compound ErV{sub 2}Al{sub 20} by specific heat and resistivity measurements. - Highlights: • Single crystals of a new compound ErV{sub 2}Al{sub 20} were grown by self-flux method. • Crystal structure is reported, based on powder x-ray diffraction. • ErV{sub 2}Al{sub 20} is a Curie-Weiss paramagnet. • Low-energy ‘rattling’ phonon mode (Θ{sub E}=44 K) is found in specific heat measurements.« less

Solution-grown crystals for neutron radiation detectors, and methods of solution growth

DOEpatents

Zaitseva, Natalia; Carman, M Leslie; Payne, Steve

2014-10-28

An organic crystal according to one embodiment includes an organic crystal comprising diphenylacetylene and stilbene or a stilbene derivative, the crystal having physical characteristics of formation from solution, the organic crystal exhibiting a signal response signature for neutrons from a radioactive source. A system according to one embodiment includes an organic crystal comprising diphenylacetylene and stilbene or a stilbene derivative, the crystal having physical characteristics of formation from solution, the organic crystal exhibiting a signal response signature for neutrons from a radioactive source; and a photodetector for detecting the signal response of the organic crystal. Methods of making such crystals are also provided.

Rheological behavior and stability of ciprofloxacin suspension: Impact of structural vehicles and flocculating agent.

PubMed

Moghimipour, Eskandar; Rezaee, Saeed; Salimi, Anayatollah; Asadi, Elham; Handali, Somayeh

2013-07-01

Ciprofloxacin is a fluoroquinolone and is used against a broad spectrum of gram-negative and gram-positive bacteria. The aim of the study is to investigate the effect of structural vehicles and other formulating factors on physical stability and rheological behavior of ciprofloxacin suspension. To formulate the suspensions, the effect of glycerin and polysorbate 80 as wetting agents was evaluated. Then to achieve controlled flocculation, different concentrations of sodium chloride and calcium chloride were added. After choosing suitable wetting and flocculating agents, structural vehicles such as sodium carboxyl methyl cellulose (NaCMC), hydroxypropylmethylcellulose (HPMC) and Veegum were evaluated. Physical stability parameters such as sedimentation volume, the degree of flocculation and the ease of redispersion of the suspensions and growth of crystals were evaluated. After incorporation of structural vehicles, the rheological properties of formulations containing were also studied to find out their rheological behavior. According to the results, suspension containing glycerin (0.2% w/v) and sodium chloride (0.05% w/v) as wetting agent and flocculating agent, respectively, were the most stable formulations regarding their F and N. Microscopic observations showed the growth of crystals in ciprofloxacin suspension in formulation without excipients and the minimum amount of crystal growth was seen in suspension containing NaCMC (0.25% w/v), Veegum (0.1% w/v) and NaCl (0.05% w/v). Rheological studies showed that almost all of the formulations had psuedoplastic behavior with different degree of thixotropy. The formulation containing NaCMC (0.25% w/v), Veegum (0.1% w/v) and NaCl (0.05% w/v) was the most stable formulation. It may be concluded that by altering the amount ratios of formulation factors, the best rheological behavior and the most proper thixotropy may be achieved.

Rheological behavior and stability of ciprofloxacin suspension: Impact of structural vehicles and flocculating agent

PubMed Central

Moghimipour, Eskandar; Rezaee, Saeed; Salimi, Anayatollah; Asadi, Elham; Handali, Somayeh

2013-01-01

Ciprofloxacin is a fluoroquinolone and is used against a broad spectrum of gram-negative and gram-positive bacteria. The aim of the study is to investigate the effect of structural vehicles and other formulating factors on physical stability and rheological behavior of ciprofloxacin suspension. To formulate the suspensions, the effect of glycerin and polysorbate 80 as wetting agents was evaluated. Then to achieve controlled flocculation, different concentrations of sodium chloride and calcium chloride were added. After choosing suitable wetting and flocculating agents, structural vehicles such as sodium carboxyl methyl cellulose (NaCMC), hydroxypropylmethylcellulose (HPMC) and Veegum were evaluated. Physical stability parameters such as sedimentation volume, the degree of flocculation and the ease of redispersion of the suspensions and growth of crystals were evaluated. After incorporation of structural vehicles, the rheological properties of formulations containing were also studied to find out their rheological behavior. According to the results, suspension containing glycerin (0.2% w/v) and sodium chloride (0.05% w/v) as wetting agent and flocculating agent, respectively, were the most stable formulations regarding their F and N. Microscopic observations showed the growth of crystals in ciprofloxacin suspension in formulation without excipients and the minimum amount of crystal growth was seen in suspension containing NaCMC (0.25% w/v), Veegum (0.1% w/v) and NaCl (0.05% w/v). Rheological studies showed that almost all of the formulations had psuedoplastic behavior with different degree of thixotropy. The formulation containing NaCMC (0.25% w/v), Veegum (0.1% w/v) and NaCl (0.05% w/v) was the most stable formulation. It may be concluded that by altering the amount ratios of formulation factors, the best rheological behavior and the most proper thixotropy may be achieved. PMID:24083201

Synthesis, Structure, and Complex Magnetism of MIr 2In 8 (M = Eu, Sr)

DOE PAGES

Calta, Nicholas P.; L. Bud’ko, Sergey; Rodriguez, Alexandra P.; ...

2016-03-07

In this paper, we report the synthesis, crystal structure, and physical properties of two new polar intermetallic compounds, EuIr 2In 8 and SrIr 2In 8. Both were synthesized in good yield using In metal as a reactive flux medium, enabling the growth of large crystals for physical property measurements. They crystallize in the orthorhombic space group Pbam with the CeFe 2Al 8 structure type, which is sometimes also referred to as the CaCo 2Al 8 structure type. The two analogues have unit cell parameters of a = 13.847(3) Å, b = 16.118(3) Å, and c = 4.3885(9) Å for Mmore » = Eu and a = 13.847(3) Å, b = 16.113(3) Å, and c = 4.3962(9) Å for M = Sr at room temperature. SrIr 2In 8 is a diamagnetic metal with no local magnetic moments on either the Sr or Ir sites, and the diamagnetic contribution from core electrons overwhelms the expected Pauli paramagnetism normally seen in intermetallic compounds. Magnetism in EuIr 2In 8 is dominated by the local Eu moments, which order antiferromagnetically at 5 K in low applied fields. Increasing the field strength depresses the magnetic ordering temperature and also induces a spin reorientation at lower temperature, indicating complex competing magnetic interactions. Finally, low-temperature heat capacity measurements show a significant enhancement of the Sommerfeld coefficient in EuIr 2In 8 relative to that in SrIr 2In 8, with estimated values of γ = 118(3) and 18.0(2) mJ mol –1 K –2, respectively.« less

INSTRUMENTS AND METHODS OF INVESTIGATION: Positron annihilation spectroscopy in materials structure studies

NASA Astrophysics Data System (ADS)

Grafutin, Viktor I.; Prokop'ev, Evgenii P.

2002-01-01

A relatively new method of materials structure analysis — positron annihilation spectroscopy (PAS) — is reviewed. Measurements of positron lifetimes, the determination of positron 3γ- and 2γ-annihilation probabilities, and an investigation of the effects of different external factors on the fundamental characteristics of annihilation constitute the basis for this promising method. The ways in which the positron annihilation process operates in ionic crystals, semiconductors, metals and some condensed matter systems are analyzed. The scope of PAS is described and its prospects for the study of the electronic and defect structures are discussed. The applications of positron annihilation spectroscopy in radiation physics and chemistry of various substances as well as in physics and chemistry of solutions are exemplified.

The effect of temperature and gas flow on the physical vapour growth of mm-scale rubrene crystals for organic FETs

NASA Astrophysics Data System (ADS)

Ullah, A. R.; Micolich, A. P.; Cochrane, J. W.; Hamilton, A. R.

2007-12-01

There has recently been significant interest in rubrene single-crystals grown using physical vapour transport techniques due to their application in high-mobility organic field-effect transistor (OFET) devices. Despite numerous studies of the electrical properties of such crystals, there has only been one study to date focussing on characterising and optimising the crystal growth as a function of the relevant growth parameters. Here we present a study of the dependence of the yield of useful crystals (defined as crystals with at least one dimension of order 1 mm) on the temperature and volume flow of carrier gas used in the physical vapour growth process.

Comparing two tetraalkylammonium ionic liquids. II. Phase transitions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lima, Thamires A.; Paschoal, Vitor H.; Faria, Luiz F. O.

Phase transitions of the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N{sub 1114}][NTf{sub 2}], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N{sub 1444}][NTf{sub 2}], were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) measurements, and Raman spectroscopy. XRD and Raman spectra were obtained as a function of temperature at atmospheric pressure, and also under high pressure at room temperature using a diamond anvil cell (DAC). [N{sub 1444}][NTf{sub 2}] experiences glass transition at low temperature, whereas [N{sub 1114}][NTf{sub 2}] crystallizes or not depending on the cooling rate. Both the ionic liquids exhibit glass transition under high pressure. XRD and low-frequency Raman spectra provide a consistent physical picturemore » of structural ordering-disordering accompanying the thermal events of crystallization, glass transition, cold crystallization, pre-melting, and melting. Raman spectra in the high-frequency range of some specific cation and anion normal modes reveal conformational changes of the molecular structures along phase transitions.« less

The cuttlefish Sepia officinalis (Sepiidae, Cephalopoda) constructs cuttlebone from a liquid-crystal precursor

PubMed Central

Checa, Antonio G.; Cartwright, Julyan H. E.; Sánchez-Almazo, Isabel; Andrade, José P.; Ruiz-Raya, Francisco

2015-01-01

Cuttlebone, the sophisticated buoyancy device of cuttlefish, is made of extensive superposed chambers that have a complex internal arrangement of calcified pillars and organic membranes. It has not been clear how this structure is assembled. We find that the membranes result from a myriad of minor membranes initially filling the whole chamber, made of nanofibres evenly oriented within each membrane and slightly rotated with respect to those of adjacent membranes, producing a helical arrangement. We propose that the organism secretes a chitin–protein complex, which self-organizes layer-by-layer as a cholesteric liquid crystal, whereas the pillars are made by viscous fingering. The liquid crystallization mechanism permits us to homologize the elements of the cuttlebone with those of other coleoids and with the nacreous septa and the shells of nautiloids. These results challenge our view of this ultra-light natural material possessing desirable mechanical, structural and biological properties, suggesting that two self-organizing physical principles suffice to understand its formation. PMID:26086668

Negative Gaussian curvature induces significant suppression of thermal conduction in carbon crystals.

PubMed

Zhang, Zhongwei; Chen, Jie; Li, Baowen

2017-09-28

From the mathematic category of surface Gaussian curvature, carbon allotropes can be classified into three types: zero curvature, positive curvature, and negative curvature. By performing Green-Kubo equilibrium molecular dynamics simulations, we found that surface curvature has a significant impact on the phonon vibration and thermal conductivity (κ) of carbon crystals. When curving from zero curvature to negative or positive curvature structures, κ is reduced by several orders of magnitude. Interestingly, we found that κ of negatively curved carbon crystals exhibits a monotonic dependence on curvature. Through phonon mode analysis, we show that curvature induces remarkable phonon softening in phonon dispersion, which results in the reduction of phonon group velocity and flattening of phonon band structure. Furthermore, the curvature was found to induce phonon mode hybridization, leading to the suppression of phonon relaxation time. Our study provides physical insight into thermal transport in curvature materials, and will be valuable in the modulation of phonon activity through surface curvature.

Fluorescence and physical properties of the organic salt 2-chloro-4-nitrobenzoate-3-ammonium-phenol

NASA Astrophysics Data System (ADS)

Mani, Rajaboopathi; Rietveld, Ivo B.; Nicolaï, Béatrice; Varadharajan, Krishnakumar; Louhi-Kultanen, Marjatta; Narasimhan, Surumbarkuzhali

2015-09-01

Organic salt 2-chloro-4-nitrobenzoate (CNBA-) 3-ammonium-phenol (AP+) exhibits fluorescence at 338 nm in solution and frontier molecular orbitals generated from TDDFT calculations indicate that the ground state and the excited state are physically separated on AP+ and CNBA-. The crystal structure and physical-chemical properties of the CNBA- · AP+ were investigated using X-ray single crystal and powder diffraction, SEM, FTIR, UV-Vis-NIR, and fluorescence spectrometry. X-ray diffraction demonstrates that the two molecules are linked via N+-H⋯O- ammonium-carboxylate interactions, as expected considering their interaction propensities. Proton transfer has been confirmed by FTIR analysis. The melting point of CNBA- · AP+ was observed at 186 °C, which is higher than pure CNBA (140 °C) or AP (120 °C). The observation of a spatially separated HOMO and LUMO possessing a narrow ΔEST = 73.3 meV and an emission in the blue region is promising as an alternative method for the production of OLED materials.

Pressure-induced nano-crystallization of silicate garnets from glass

PubMed Central

Irifune, T.; Kawakami, K.; Arimoto, T.; Ohfuji, H.; Kunimoto, T.; Shinmei, T.

2016-01-01

Transparent ceramics are important for scientific and industrial applications because of the superior optical and mechanical properties. It has been suggested that optical transparency and mechanical strength are substantially enhanced if transparent ceramics with nano-crystals are available. However, synthesis of the highly transparent nano-crystalline ceramics has been difficult using conventional sintering techniques at relatively low pressures. Here we show direct conversion from bulk glass starting material in mutianvil high-pressure apparatus leads to pore-free nano-polycrystalline silicate garnet at pressures above ∼10 GPa in a limited temperature range around 1,400 °C. The synthesized nano-polycrystalline garnet is optically as transparent as the single crystal for almost the entire visible light range and harder than the single crystal by ∼30%. The ultrahigh-pressure conversion technique should provide novel functional ceramics having various crystal structures, including those of high-pressure phases, as well as ideal specimens for some mineral physics applications. PMID:27924866

Growth and characterization of CaFe1-xCoxAsF single crystals by CaAs flux method

NASA Astrophysics Data System (ADS)

Ma, Yonghui; Hu, Kangkang; Ji, Qiucheng; Gao, Bo; Zhang, Hui; Mu, Gang; Huang, Fuqiang; Xie, Xiaoming

2016-10-01

Millimeter sized single crystals of CaFe1-x Cox AsF were grown using a self-flux method. It is found that high-quality single crystals can be grown from three approaches with different initial raw materials. The chemical compositions and crystal structure were characterized carefully. Compared with the undoped parent phase CaFeAsF, the crystal lattice along the c-axis is suppressed by the Co substitution while that along the a-axis expands slightly. Superconductivity with the critical transition Tc as high as 21 K was confirmed by both the resistivity and magnetic susceptibility measurements in the sample with x=0.118. Moreover, it is found that Tc can be enhanced for about 1 K under the very small hydrostatic pressure of 0.22 GPa, which is more quick than that reported in the polycrystalline samples. Our results are a promotion for the physical investigations of 1111 phase iron-pnictide superconductors.

Photonic crystals possessing multiple Weyl points and the experimental observation of robust surface states

PubMed Central

Chen, Wen-Jie; Xiao, Meng; Chan, C. T.

2016-01-01

Weyl points, as monopoles of Berry curvature in momentum space, have captured much attention recently in various branches of physics. Realizing topological materials that exhibit such nodal points is challenging and indeed, Weyl points have been found experimentally in transition metal arsenide and phosphide and gyroid photonic crystal whose structure is complex. If realizing even the simplest type of single Weyl nodes with a topological charge of 1 is difficult, then making a real crystal carrying higher topological charges may seem more challenging. Here we design, and fabricate using planar fabrication technology, a photonic crystal possessing single Weyl points (including type-II nodes) and multiple Weyl points with topological charges of 2 and 3. We characterize this photonic crystal and find nontrivial 2D bulk band gaps for a fixed kz and the associated surface modes. The robustness of these surface states against kz-preserving scattering is experimentally observed for the first time. PMID:27703140

Segregation of liquid crystal mixtures in topological defects

DOE PAGES

Rahimi, Mohammad; Ramezani-Dakhel, Hadi; Zhang, Rui; ...

2017-04-28

The structure and physical properties of liquid crystal (LC) mixtures are a function of composition, and small changes can have pronounced effects on observables, such as phase-transition temperatures. Traditionally, LC mixtures have been assumed to be compositionally homogenous. The results of chemically detailed simulations presented here show that this is not the case; pronounced deviations of the local order from that observed in the bulk at defects and interfaces lead to significant compositional segregation effects. More specifically, two disclination lines are stabilized in this work by introducing into a nematic liquid crystal mixture a cylindrical body that exhibits perpendicular anchoring.more » Here, it is found that the local composition deviates considerably from that of the bulk at the interface with the cylinder and in the defects, thereby suggesting new assembly and synthetic strategies that may capitalize on the unusual molecular environment provided by liquid crystal mixtures.« less

A new organic superconductor, beta-(BDA-TTP)2GaCl4 [BDA-TTP = 2,5-(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene].

PubMed

Yamada, Jun-ichi; Toita, Takashi; Akutsu, Hiroki; Nakatsuji, Shin'ichi; Nishikawa, Hiroyuki; Ikemoto, Isao; Kikuchi, Koichi; Choi, Eun S; Graf, David; Brooks, James S

2003-09-07

The preparation, crystal structure and physical properties of beta-(BDA-TTP)2GaCl4 has been investigated; the salt exhibits superconductivity at 3.1 K (onset) under a hydrostatic pressure of 7.6 kbar.

Mixed crystal organic scintillators

DOEpatents

Zaitseva, Natalia P; Carman, M Leslie; Glenn, Andrew M; Hamel, Sebastien; Hatarik, Robert; Payne, Stephen A; Stoeffl, Wolfgang

2014-09-16

A mixed organic crystal according to one embodiment includes a single mixed crystal having two compounds with different bandgap energies, the organic crystal having a physical property of exhibiting a signal response signature for neutrons from a radioactive source, wherein the signal response signature does not include a significantly-delayed luminescence characteristic of neutrons interacting with the organic crystal relative to a luminescence characteristic of gamma rays interacting with the organic crystal. According to one embodiment, an organic crystal includes bibenzyl and stilbene or a stilbene derivative, the organic crystal having a physical property of exhibiting a signal response signature for neutrons from a radioactive source.

Generalized Finsler geometric continuum physics with applications in fracture and phase transformations

NASA Astrophysics Data System (ADS)

Clayton, J. D.

2017-02-01

A theory of deformation of continuous media based on concepts from Finsler differential geometry is presented. The general theory accounts for finite deformations, nonlinear elasticity, and changes in internal state of the material, the latter represented by elements of a state vector of generalized Finsler space whose entries consist of one or more order parameter(s). Two descriptive representations of the deformation gradient are considered. The first invokes an additive decomposition and is applied to problems involving localized inelastic deformation mechanisms such as fracture. The second invokes a multiplicative decomposition and is applied to problems involving distributed deformation mechanisms such as phase transformations or twinning. Appropriate free energy functions are posited for each case, and Euler-Lagrange equations of equilibrium are derived. Solutions are obtained for specific problems of tensile fracture of an elastic cylinder and for amorphization of a crystal under spherical and uniaxial compression. The Finsler-based approach is demonstrated to be more general and potentially more physically descriptive than existing hyperelasticity models couched in Riemannian geometry or Euclidean space, without incorporation of supplementary ad hoc equations or spurious fitting parameters. Predictions for single crystals of boron carbide ceramic agree qualitatively, and in many instances quantitatively, with results from physical experiments and atomic simulations involving structural collapse and failure of the crystal along its c-axis.

Orbital angular momentum light frequency conversion and interference with quasi-phase matching crystals.

PubMed

Zhou, Zhi-Yuan; Ding, Dong-Sheng; Jiang, Yun-Kun; Li, Yan; Shi, Shuai; Wang, Xi-Shi; Shi, Bao-Sen

2014-08-25

Light with helical phase structures, carrying quantized orbital angular momentum (OAM), has many applications in both classical and quantum optics, such as high-capacity optical communications and quantum information processing. Frequency conversion is a basic technique to expand the frequency range of the fundamental light. The frequency conversion of OAM-carrying light gives rise to new physics and applications such as up-conversion detection of images and generation of high dimensional OAM entanglements. Quasi-phase matching (QPM) nonlinear crystals are good candidates for frequency conversion, particularly due to their high-valued effective nonlinear coefficients and no walk-off effect. Here we report the first experimental second-harmonic generation (SHG) of an OAM-carried light with a QPM crystal, where a UV light with OAM of 100 ℏ is generated. OAM conservation is verified using a specially designed interferometer. With a pump beam carrying an OAM superposition of opposite sign, we observe interesting interference phenomena in the SHG light; specifically, a photonics gear-like structure is obtained that gives direct evidence of OAM conservation, which will be very useful for ultra-sensitive angular measurements. Besides, we also develop a theory to reveal the underlying physics of the phenomena. The methods and theoretical analysis shown here are also applicable to other frequency conversion processes, such as sum frequency generation and difference-frequency generation, and may also be generalized to the quantum regime for single photons.

Synthesis and Properties of Dodecyl Trehaloside Detergents for Membrane Protein Studies

PubMed Central

Tao, Houchao; Fu, Yu; Thompson, Aaron; Lee, Sung Chang; Mahoney, Nicholas; Stevens, Raymond C.; Zhang, Qinghai

2012-01-01

Sugar-based detergents, mostly derived from maltose or glucose, prevail in the extraction, solubilization, stabilization and crystallization of membrane proteins. Inspired by the broad use of trehalose for protecting biological macromolecules and lipid bilayer structures, we synthesized new trehaloside detergents for potential applications in membrane protein research. We devised an efficient synthesis of four dodecyl trehalosides, each with the 12-carboned alkyl chain attached to different hydroxyl groups of trehalose, thus presenting a structurally diverse but related family of detergents. The detergent physical properties, including solubility, hydrophobicity, critical micelle concentration (CMC) and size of micelles, were evaluated and compared with the most popular maltoside analog, β- D-dodecylmaltoside (DDM), which varied from each other due to distinct molecular geometries and possible polar group interactions in resulting micelles. Crystals of 2-dodecyl trehaloside (2-DDTre) were also obtained in methanol, and the crystal packing revealed multiple H-bonded interactions among adjacent trehalose groups. The few trehaloside detergents were tested for the solubilization and stabilization of the nociceptin/orphanin FQ peptide receptor (ORL1) and MsbA, which belong to the G-protein coupled receptor (GPCR) and ATP-binding cassette transporter families, respectively. Our results demonstrated the utility of trehaloside detergents as membrane protein solubilization reagents with the optimal detergents being protein dependent. Continuing development and investigations of trehaloside detergents are attractive given their interesting and unique chemical-physical properties and potential interactions with membrane lipids. PMID:22780816

Helical Growth of Aluminum Nitride: New Insights into Its Growth Habit from Nanostructures to Single Crystals

PubMed Central

Zhang, Xing-Hong; Shao, Rui-Wen; Jin, Lei; Wang, Jian-Yu; Zheng, Kun; Zhao, Chao-Liang; Han, Jie-Cai; Chen, Bin; Sekiguchi, Takashi; Zhang, Zhi; Zou, Jin; Song, Bo

2015-01-01

By understanding the growth mechanism of nanomaterials, the morphological features of nanostructures can be rationally controlled, thereby achieving the desired physical properties for specific applications. Herein, the growth habits of aluminum nitride (AlN) nanostructures and single crystals synthesized by an ultrahigh-temperature, catalyst-free, physical vapor transport process were investigated by transmission electron microscopy. The detailed structural characterizations strongly suggested that the growth of AlN nanostructures including AlN nanowires and nanohelixes follow a sequential and periodic rotation in the growth direction, which is independent of the size and shape of the material. Based on these experimental observations, an helical growth mechanism that may originate from the coeffect of the polar-surface and dislocation-driven growth is proposed, which offers a new insight into the related growth kinetics of low-dimensional AlN structures and will enable the rational design and synthesis of novel AlN nanostructures. Further, with the increase of temperature, the growth process of AlN grains followed the helical growth model. PMID:25976071

Towards engineered branch placement: Unreal™ match between vapour-liquid-solid glancing angle deposition nanowire growth and simulation

NASA Astrophysics Data System (ADS)

Taschuk, M. T.; Tucker, R. T.; LaForge, J. M.; Beaudry, A. L.; Kupsta, M. R.; Brett, M. J.

2013-12-01

The vapour-liquid-solid glancing angle deposition (VLS-GLAD) process is capable of producing complex nanotree structures with control over azimuthal branch orientation and height. We have developed a thin film growth simulation including ballistic deposition, simplified surface diffusion, and droplet-mediated cubic crystal growth for the VLS-GLAD process using the UnrealTM Development Kit. The use of a commercial game engine has provided an interactive environment while allowing a custom physics implementation. Our simulation's output is verified against experimental data, including a volumetric film reconstruction produced using focused ion beam and scanning-electron microscopy (SEM), crystallographic texture, and morphological characteristics such as branch orientation. We achieve excellent morphological and texture agreement with experimental data, as well as qualitative agreement with SEM imagery. The simplified physics in our model reproduces the experimental films, indicating that the dominant role flux geometry plays in the VLS-GLAD competitive growth process responsible for azimuthally oriented branches and biaxial crystal texture evolution. The simulation's successful reproduction of experimental data indicates that it should have predictive power in designing novel VLS-GLAD structures.

Atomic electron tomography: 3D structures without crystals

DOE PAGES

Miao, Jianwei; Ercius, Peter; Billinge, S. J. L.

2016-09-23

Crystallography has been fundamental to the development of many fields of science over the last century. However, much of our modern science and technology relies on materials with defects and disorders, and their three-dimensional (3D) atomic structures are not accessible to crystallography. One method capable of addressing this major challenge is atomic electron tomography. By combining advanced electron microscopes and detectors with powerful data analysis and tomographic reconstruction algorithms, it is now possible to determine the 3D atomic structure of crystal defects such as grain boundaries, stacking faults, dislocations, and point defects, as well as to precisely localize the 3Dmore » coordinates of individual atoms in materials without assuming crystallinity. In this work, we review the recent advances and the interdisciplinary science enabled by this methodology. We also outline further research needed for atomic electron tomography to address long-standing unresolved problems in the physical sciences.« less

The effect of a solid surface on the segregation and melting of salt hydrates.

PubMed

Zhang, Yu; Anim-Danso, Emmanuel; Dhinojwala, Ali

2014-10-22

Considering the importance of salt and water on earth, the crystallization of salt hydrates next to solid surfaces has important implications in physical and biological sciences. Heterogeneous nucleation is driven by surface interactions, but our understanding of hydrate formation near surfaces is limited. Here, we have studied the hydrate formation of three commonly prevalent salts, MgCl2, CaCl2, and NaCl, next to a sapphire substrate using surface sensitive infrared-visible sum frequency generation (SFG) spectroscopy. SFG spectroscopy can detect the crystallization and melting of salt hydrates at the interface by observing the changes in the intensity and the location of the cocrystallized water hydroxyl peaks (3200-3600 cm(-1)). The results indicate that the surface crystal structures of these three hydrates are similar to those in the bulk. For the NaCl solution, the brine solution is segregated next to the sapphire substrate after the formation of the ice phase. In contrast, the MgCl2 and CaCl2 surface hydrate crystals are interdispersed with nanometer-size ice crystals. The nanosize ice crystals melt at much lower temperatures than bulk ice crystals. For NaCl and MgCl2 solution, the NaCl hydrates prefer to crystallize next to the sapphire substrate instead of the ice crystals and MgCl2 hydrates.

Strain history of ice shells of the Galilean satellites from radar detection of crystal orientation fabric

NASA Astrophysics Data System (ADS)

Barr, Amy C.; Stillman, David E.

2011-03-01

Orbital radar sounding has been suggested as a means of determining the subsurface thermal and physical structure of the outer ice I shells of the Galilean satellites. At radar frequencies, the dielectric permittivity of single- and polycrystalline water ice I is anisotropic. Crystal orientation fabric (COF), which is indicative of strain history, can be unambiguously detected by comparing the received power of dual co-polarization (linear polarization parallel and perpendicular to the orbit) radar data. Regions with crystal orientations dictated by the local strain field (“fabric”) form in terrestrial ice masses where accumulated strain and temperature are high, similar to conditions expected in a convecting outer ice I shell on Europa, Ganymede, or Callisto. We use simulations of solid-state ice shell convection to show that crystal orientation fabric can form in the warm convecting sublayer of the ice shells for plausible grain sizes. Changes in received power from parallel and perpendicular polarizations in the ice shells due to fabric could be detected if multi-polarization data is collected. With proper instrument design, radar sounding could be used to shed light on the strain history of the satellites' ice shells in addition to their present day internal structures.

Transmission property of the one-dimensional phononic crystal thin plate by the eigenmode matching theory

NASA Astrophysics Data System (ADS)

Hou, Zhilin; Assouar, Badreddine M.

2008-05-01

Eigenmode matching theory, which was developed originally for the band structure and the transmission property of the infinite phononic crystal (PC), is extended to deal with the PC thin plate. By this method, the transmission property of the one-dimensional PC thin plate with and without a uniform substrate is investigated. It is shown that in the PC thin plate without a substrate, the permitted band of the structure can be separated into two parts, which can be excited by the incident antisymmetric and symmetric Lamb modes, respectively. However, for the PC plate with a substrate, the energy conversion between the symmetric and antisymmetric modes can be found in the transmission spectrum. The physical origin of such an energy conversion is discussed.

A Crystal-Physical Model of Electrotransfer in the Superionic Conductor Pb1 - x Sc x F2 + x ( x = 0.1)

NASA Astrophysics Data System (ADS)

Sorokin, N. I.

2018-04-01

The frequency (ν = 10-1-107 Hz) dependences of electrical conductivity σ(ν) of single crystals of superionic conductor Pb0.9Sc0.1F2.1 (10 mol % ScF3) with fluorite type structure (CaF2) in the temperature range 153-410 K have been investigated. The static bulk conductivity σ dc =1.5 × 10-4 S/cm and average hopping frequency ν h = 1.5 × 107 Hz of charge carriers (mobile ions F-) at room temperature (293 K) have been defined from the σ dc (ν) experimental curves. Enthalpies of thermoactivated processes of ionic conductivity σ dc ( T) (Δ H σ = 0.393 ± 0.005 eV) and dielectric relaxation ν h ( T) (Δ H h = 0.37 ± 0.03 eV) coincide within their errors. A crystal-physical model of fluorine-ion transport in a Pb0.9Sc0.1F2.1 crystal lattice has been proposed. The characteristic parameters of charge carriers have been calculated: concentration n mob = 2.0 × 1021 cm-3, the distance of the hopping d ≈ 0.5 nm and mobility μmob = 4.5 × 10-7 cm2/s V (293 K).

Diffusion-controlled and "diffusionless" crystal growth near the glass transition temperature: relation between liquid dynamics and growth kinetics of seven ROY polymorphs.

PubMed

Sun, Ye; Xi, Hanmi; Ediger, M D; Richert, Ranko; Yu, Lian

2009-08-21

The liquid dynamics of 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile, named ROY for its red, orange, and yellow crystal polymorphs, was characterized by dielectric spectroscopy and differential scanning calorimetry. Four of these polymorphs show fast "diffusionless" crystal growth at low temperatures while three others do not. ROY was found to be a typical fragile organic liquid. Its alpha relaxation process has time-temperature superposition symmetry across the viscous range (tau(alpha)=100 s-100 ns) with the width of the relaxation peak characterized by a constant beta(KWW) of 0.73. No secondary relaxation peak was observed, even with glasses made by fast quenching. For the polymorphs not showing fast crystal growth in the glassy state, the growth rate has a power-law relation with tau(alpha), u proportional to tau(alpha)(-xi), where xi approximately = 0.7. For the polymorphs showing fast crystal growth in the glassy state, the growth is so fast near and below the glass transition temperature T(g) that thousands of molecular layers can be added to the crystalline phase during one structural relaxation time of the liquid. In the glassy state, this mode of growth slows slightly over time. This slowdown is not readily explained by the effect of physical aging on the thermodynamic driving force of crystallization, the glass vapor pressure, or the rate of structural relaxation. This study demonstrates that from the same liquid or glass, the growth of some polymorphs is accurately described as being limited by the rate of structural relaxation or bulk diffusion, whereas the growth of other polymorphs is too fast to be under such control.

Sun protection enhancement of titanium dioxide crystals by the use of carnauba wax nanoparticles: the synergistic interaction between organic and inorganic sunscreens at nanoscale.

PubMed

Villalobos-Hernández, J R; Müller-Goymann, C C

2006-09-28

Carnauba wax is partially composed of cinnamates. The rational combination of cinnamates and titanium dioxide has shown a synergistic effect to improve the sun protection factor (SPF) of cosmetic preparations. However, the mechanism of this interaction has not been fully understood. In this study, an ethanolic extract of the carnauba wax and an ethanolic solution of a typical cinnamate derivative, ethylcinnamate, were prepared and their UV absorption and SPF either alone or in the presence of titanium dioxide were compared. The titanium dioxide crystals and the cinnamates solutions were also distributed into a matrix composed of saturated fatty acids to emulate the structure of the crystallized carnauba wax. SPF, differential scanning calorimetry (DSC) and X-ray studies of these matrices were performed. Additionally, carnauba wax nanosuspensions containing titanium dioxide either in the lipid phase or in the aqueous phase were prepared to evaluate their SPFs and their physical structure. Strong UV absorption was observed in diluted suspensions of titanium dioxide after the addition of cinnamates. The saturated fatty acid matrices probably favored the adsorption of the cinnamates at the surface of titanium dioxide crystals, which was reflected by an increase in the SPF. No modification of the crystal structure of the fatty acid matrices was observed after the addition of cinnamates or titanium dioxide. The distribution of the titanium dioxide inside the lipid phase of the nanosuspensions was more effective to reach higher SPFs than that at the aqueous phase. The close contact between the carnauba wax and the titanium dioxide crystals after the high-pressure homogenization process was confirmed by transmission electron microscopy (TEM).

Light Microscopy Module: An On-Orbit Microscope Planned for the Fluids and Combustion Facility on the International Space Station

NASA Technical Reports Server (NTRS)

Doherty, Michael P.; Motil, Susan M.; Snead, John H.; Griffin, DeVon W.

2001-01-01

The Light Microscopy Module (LMM) is planned as a fully remotely controllable on-orbit microscope subrack facility, allowing flexible scheduling and control of fluids and biology experiments within NASA Glenn Research Center's Fluids and Combustion Facility on the International Space Station. Within the Fluids and Combustion Facility, four fluids physics experiments will utilize an instrument built around a light microscope. These experiments are the Constrained Vapor Bubble experiment (Peter C. Wayner of Rensselaer Polytechnic Institute), the Physics of Hard Spheres Experiment-2 (Paul M. Chaikin of Princeton University), the Physics of Colloids in Space-2 experiment (David A. Weitz of Harvard University), and the Low Volume Fraction Colloidal Assembly experiment (Arjun G. Yodh of the University of Pennsylvania). The first experiment investigates heat conductance in microgravity as a function of liquid volume and heat flow rate to determine, in detail, the transport process characteristics in a curved liquid film. The other three experiments investigate various complementary aspects of the nucleation, growth, structure, and properties of colloidal crystals in microgravity and the effects of micromanipulation upon their properties. Key diagnostic capabilities for meeting the science requirements of the four experiments include video microscopy to observe sample features including basic structures and dynamics, interferometry to measure vapor bubble thin film thickness, laser tweezers for colloidal particle manipulation and patterning, confocal microscopy to provide enhanced three-dimensional visualization of colloidal structures, and spectrophotometry to measure colloidal crystal photonic properties.

Rattling induced superconductivity in RV2Al20 (R = Sc, Lu, Y) aluminides - an experimental and theoretical study

NASA Astrophysics Data System (ADS)

Winiarski, Michal; Wiendlocha, Bartlomiej; Sternik, Malgorzata; Wisniewski, Piotr; Kaczorowski, Dariusz; Klimczuk, Tomasz

Polycrystalline samples of four ternary intermetallics RV2Al20 (R = Sc, Y, La, and Lu) were synthesized. Structural studies carried out using powder x-ray diffraction and Rietveld analysis show that all compounds crystallize in CeCr2Al20-type structure composed of icosahedral Al-R cages. Results of physical properties measurements reveal that ScV2Al20, YV2Al20, and LuV2Al20 are weakly-coupled BCS superconductors with critical temperatures Tc = 1.0, 0.57, and 0.60 K, respectively. Electronic and phonon structure calculations reveal the key role of low-frequency anharmonic vibrations of R atoms (rattling effect) for the appearance of superconductivity. A correlation between phonon and crystal structures was observed, allowing to search for new RV2Al20 superconductors. Project was financially supported by the National Science Centre (Poland) Grant (DEC-2012/07/E/ST3/00584).

Repulsive Guidance Molecule is a structural bridge between Neogenin and Bone Morphogenetic Protein

PubMed Central

Healey, Eleanor G.; Bishop, Benjamin; Elegheert, Jonathan; Bell, Christian H.; Padilla-Parra, Sergi; Siebold, Christian

2015-01-01

Repulsive guidance molecules (RGMs) control crucial processes spanning cell motility, adhesion, immune cell regulation and systemic iron metabolism. RGMs signal via two fundamental signaling cascades: the Neogenin (NEO1) and the Bone Morphogenetic Protein (BMP) pathways. Here, we report crystal structures of the N-terminal domains of all human RGM family members in complex with the BMP ligand BMP2, revealing a novel protein fold and a conserved BMP-binding mode. Our structural and functional data suggest a pH-linked mechanism for RGM-activated BMP signaling and offer a rationale for RGM mutations causing juvenile hemochromatosis. We also determined the ternary BMP2–RGM–NEO1 complex crystal structure, which combined with solution scattering and live-cell super-resolution fluorescence microscopy, indicates BMP-induced clustering of the RGM–NEO1 complex. Our results show how RGM acts as the central hub linking BMP and NEO1 and physically connecting these fundamental signaling pathways. PMID:25938661

Infrared light-induced protein crystallization. Structuring of protein interfacial water and periodic self-assembly

NASA Astrophysics Data System (ADS)

Kowacz, Magdalena; Marchel, Mateusz; Juknaité, Lina; Esperança, José M. S. S.; Romão, Maria João; Carvalho, Ana Luísa; Rebelo, Luís Paulo N.

2017-01-01

We show that a physical trigger, a non-ionizing infrared (IR) radiation at wavelengths strongly absorbed by liquid water, can be used to induce and kinetically control protein (periodic) self-assembly in solution. This phenomenon is explained by considering the effect of IR light on the structuring of protein interfacial water. Our results indicate that the IR radiation can promote enhanced mutual correlations of water molecules in the protein hydration shell. We report on the radiation-induced increase in both the strength and cooperativeness of H-bonds. The presence of a structured dipolar hydration layer can lead to attractive interactions between like-charged biomacromolecules in solution (and crystal nucleation events). Furthermore, our study suggests that enveloping the protein within a layer of structured solvent (an effect enhanced by IR light) can prevent the protein non-specific aggregation favoring periodic self-assembly. Recognizing the ability to affect protein-water interactions by means of IR radiation may have important implications for biological and bio-inspired systems.

Design of radial phononic crystal using annular soft material with low-frequency resonant elastic structures

NASA Astrophysics Data System (ADS)

Gao, Nansha; Wu, Jiu Hui; Yu, Lie; Xin, Hang

2016-10-01

Using FEM, we theoretically study the vibration properties of radial phononic crystal (RPC) with annular soft material. The band structures, transmission spectra, and displacement fields of eigenmode are given to estimate the starting and cut-off frequency of band gaps. Numerical calculation results show that RPC with annular soft material can yield low-frequency band gaps below 350 Hz. Annular soft material decreases equivalent stiffness of the whole structure effectively, and makes corresponding band gaps move to the lower frequency range. Physical mechanism behind band gaps is the coupling effect between long or traveling wave in plate matrix and the vibrations of corrugations. By changing geometrical dimensions of plate thickness e, the length of silicone rubber h2, and the corrugation width b, we can control the location and width of the first band gap. These research conclusions of RPC structure with annular soft material can potentially be applied to optimize band gaps, generate filters, and design acoustic devices.

Anisotropic physical properties of single-crystal U2Rh2Sn in high magnetic fields

NASA Astrophysics Data System (ADS)

Prokeš, K.; Gorbunov, D. I.; Reehuis, M.; Klemke, B.; Gukasov, A.; Uhlířová, K.; Fabrèges, X.; Skourski, Y.; Yokaichiya, F.; Hartwig, S.; Andreev, A. V.

2017-05-01

We report on the crystal and magnetic structures, magnetic, transport, and thermal properties of U2Rh2Sn single crystals studied in part in high magnetic fields up to 58 T. The material adopts a U3Si2 -related tetragonal crystal structure and orders antiferromagnetically below TN=25 K. The antiferromagnetic structure is characterized by a propagation vector k =(00 1/2 ) . The magnetism in U2Rh2Sn is found to be associated mainly with 5 f states. However, both unpolarized and polarized neutron experiments reveal at low temperatures in zero field non-negligible magnetic moments also on Rh sites. U moments of 0.50(2) μB are directed along the tetragonal axis while Rh moments of 0.06(4) μB form a noncollinear arrangement confined to the basal plane. The response to applied magnetic field is highly anisotropic. Above ˜15 K the easy magnetization direction is along the tetragonal axis. At lower temperatures, however, a stronger response is found perpendicular to the c axis. While for the a axis no magnetic phase transition is observed up to 58 T, for the field applied at 1.8 K along the tetragonal axis we observe above 22.5 T a field-polarized state. A magnetic phase diagram for the field applied along the c axis is presented.

Roles of bond orientational ordering in glass transition and crystallization.

PubMed

Tanaka, Hajime

2011-07-20

It is widely believed that crystallization in three dimensions is primarily controlled by positional ordering, and not by bond orientational ordering. In other words, bond orientational ordering is usually considered to be merely a consequence of positional ordering and thus has often been ignored. This one-order-parameter (density) description may be reasonable when we consider an equilibrium liquid-solid transition, but may not be enough to describe a metastable state and the kinetics of the transition. Here we propose that bond orientational ordering can play a key role in (i) crystallization, (ii) the ordering to quasi-crystal and (iii) vitrification, which occurs under rather weak frustration against crystallization. In a metastable supercooled state before crystallization, a system generally tends to have bond orientational order at least locally as a result of a constraint of dense packing. For a system interacting with hard-core repulsions, the constraint is intrinsically of geometrical origin and thus the basic physics is the same as nematic ordering of rod-like particles upon densification. Furthermore, positional ordering is easily destroyed even by weak frustration such as polydispersity and anisotropic interactions which favour a symmetry not consistent with that of the equilibrium crystal. Thus we may say that vitrification can be achieved by disturbing and prohibiting long-range positional ordering. Even in such a situation, bond orientational ordering still survives, accompanying its critical-like fluctuations, which are the origin of dynamic heterogeneity for this case. This scenario naturally explains both the absence of positional order and the development of bond orientational order upon cooling in a supercooled state. Although our argument is speculative in nature, we emphasize that this physical picture can coherently explain crystallization, vitrification, quasi-crystallization and their relationship in a natural manner. For a strongly frustrated system, even bond orientational order can be destroyed. Even in such a case there may still appear a structural signature of dense packing, which is linked to slow dynamics.

Modulus and yield stress of drawn LDPE

NASA Astrophysics Data System (ADS)

Thavarungkul, Nandh

Modulus and yield stress were investigated in drawn low density polyethylene (LDPE) film. Uniaxially drawn polymeric films usually show high values of modulus and yield stress, however, studies have normally only been conducted to identify the structural features that determine modulus. In this study small-angle x-ray scattering (SAXS), thermal shrinkage, birefringence, differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA) were used to examine, directly and indirectly, the structural features that determine both modulus and yield stress, which are often closely related in undrawn materials. Shish-kebab structures are proposed to account for the mechanical properties in drawn LDPE. The validity of this molecular/morphological model was tested using relationships between static mechanical data and structural and physical parameters. In addition, dynamic mechanical results are also in line with static data in supporting the model. In the machine direction (MD), "shish" and taut tie molecules (TTM) anchored in the crystalline phase account for E; whereas crystal lamellae with contributions from "shish" and TTM determine yield stress. In the transverse direction (TD), the crystalline phase plays an important roll in both modulus and yield stress. Modulus is determined by crystal lamellae functioning as platelet reinforcing elements in the amorphous matrix with an additional contributions from TTM and yield stress is determined by the crystal lamellae's resistance to deformation.

Quasi-periodic photonic crystal Fabry–Perot optical filter based on Si/SiO2 for visible-laser spectral selectivity

NASA Astrophysics Data System (ADS)

Qi, Dong; Wang, Xian; Cheng, Yongzhi; Chen, Fu; Liu, Lei; Gong, Rongzhou

2018-06-01

We report on a 1D quasi-periodic photonic crystal Fabry–Perot optical filter Cs(Si/SiO2)3(SiO2/Si)3 for spectral selectivity of visible light and 1.55 µm laser. A material transparency interval of 1.03–2.06 µm makes Si a unique choice of high refractive index material. Owing to the CIE 1931 standard and equal inclination interference, the designed structure can be successfully fabricated with a certain color (brown, khaki, or blue) corresponding to the different Cs physical thickness d and response R(λ). In addition, the peak transmittance T max of the proposed structure can reach as high as 92.56% (Cs  =  20 nm), 90.83% (Cs  =  40 nm), and 88.85% (Cs  =  60 nm) with a relatively narrow full width at half maximum of 4.4, 4.6, and 4.8 nm at 1.55 µm. The as-prepared structure indicates that it is feasible for a photonic crystal Fabry–Perot optical filter to achieve visible-laser (1.55 µm) spectral selectivity.

First principles investigations of vinazene molecule and molecular crystal: a prospective candidate for organic photovoltaic applications.

PubMed

Mohamad, Mazmira; Ahmed, Rashid; Shaari, Amirudin; Goumri-Said, Souraya

2015-02-01

Escalating demand for sustainable energy resources, because of the rapid exhaustion of conventional energy resources as well as to maintain the environmental level of carbon dioxide (CO2) to avoid its adverse effect on the climate, has led to the exploitation of photovoltaic technology manifold more than ever. In this regard organic materials have attracted great attention on account of demonstrating their potential to harvest solar energy at an affordable rate for photovoltaic technology. 2-vinyl-4,5-dicyanoimidazole (vinazene) is considered as a suitable material over the fullerenes for photovoltaic applications because of its particular chemical and physical nature. In the present study, DFT approaches are employed to provide an exposition of optoelectronic properties of vinazene molecule and molecular crystal. To gain insight into its properties, different forms of exchange correlation energy functional/potential such as LDA, GGA, BLYP, and BL3YP are used. Calculated electronic structure of vinazene molecule has been displayed via HOMO-LUMO isosurfaces, whereas electronic structure of the vinazene molecular crystal, via electronic band structure, is presented. The calculated electronic and optical properties were analyzed and compared as well. Our results endorse vinazene as a suitable material for organic photovoltaic applications.

Electromagnetic density of modes for a finite-size three-dimensional structure.

PubMed

D'Aguanno, Giuseppe; Mattiucci, Nadia; Centini, Marco; Scalora, Michael; Bloemer, Mark J

2004-05-01

The concept of the density of modes has been lacking a precise mathematical definition for a finite-size structure. With the explosive growth in the fabrication of photonic crystals and nanostructures, which are inherently finite in size, a workable definition is imperative. We give a simple and physically intuitive definition of the electromagnetic density of modes based on the Green's function for a generic three-dimensional open cavity filled with a linear, isotropic, dielectric material.

Plaster-based magnetite composite materials in construction

NASA Astrophysics Data System (ADS)

Klimenko, V. G.; Kashin, G. A.; Prikaznova, T. A.

2018-03-01

Calculation and experimental data demonstrate the possibility of using iron-ore concentrate of Lebedinsky Mining and Processing Plant (Lebedinsky GOK) in the production of plaster concrete. Their physical-mechanical, thermal and radiation protective properties were studied. Structurization mechanisms in plaster magnetite systems depending on the type of plaster binder, textures and the structure of plaster crystals providing for the design of composite materials with predetermined properties are suggested. Composite materials to ensure protection against X-ray radiation are obtained.

Features of structure-phase transformations and segregation processes under irradiation of austenitic and ferritic-martensitic steels

NASA Astrophysics Data System (ADS)

Neklyudov, I. M.; Voyevodin, V. N.

1994-09-01

The difference between crystal lattices of austenitic and ferritic steels leads to distinctive features in mechanisms of physical-mechanical change. This paper presents the results of investigations of dislocation structure and phase evolution, and segregation phenomena in austenitic and ferritic-martensitic steels and alloys during irradiation with heavy ions in the ESUVI and UTI accelerators and by neutrons in fast reactors BOR-60 and BN-600. The influence of different factors (including different alloying elements) on processes of structure-phase transformation was studied.

Time-resolved Sensing of Meso-scale Shock Compression with Multilayer Photonic Crystal Structures

NASA Astrophysics Data System (ADS)

Scripka, David; Lee, Gyuhyon; Summers, Christopher J.; Thadhani, Naresh

2017-06-01

Multilayer Photonic Crystal structures can provide spatially and temporally resolved data needed to validate theoretical and computational models relevant for understanding shock compression in heterogeneous materials. Two classes of 1-D photonic crystal multilayer structures were studied: optical microcavities (OMC) and distributed Bragg reflectors (DBR). These 0.5 to 5 micron thick structures were composed of SiO2, Al2O3, Ag, and PMMA layers fabricated primarily via e-beam evaporation. The multilayers have unique spectral signatures inherently linked to their time-resolved physical states. By observing shock-induced changes in these signatures, an optically-based pressure sensor was developed. Results to date indicate that both OMCs and DBRs exhibit nanosecond-resolved spectral shifts of several to 10s of nanometers under laser-driven shock compression loads of 0-10 GPa, with the magnitude of the shift strongly correlating to the shock load magnitude. Additionally, spatially and temporally resolved spectral shifts under heterogeneous laser-driven shock compression created by partial beam blocking have been successfully demonstrated. These results illustrate the potential for multilayer structures to serve as meso-scale sensors, capturing temporal and spatial pressure profile evolutions in shock-compressed heterogeneous materials, and revealing meso-scale pressure distributions across a shocked surface. Supported by DTRA Grant HDTRA1-12-1-005 and DoD, AFOSR, National Defense Science and Eng. Graduate Fellowship, 32 CFR 168a.

Two new phases in the ternary RE-Ga-S systems with the unique interlinkage of GaS4 building units: synthesis, structure, and properties.

PubMed

Lin, Hua; Shen, Jin-Ni; Zhu, Wei-Wei; Liu, Yi; Wu, Xin-Tao; Zhu, Qi-Long; Wu, Li-Ming

2017-10-17

Two novel ternary rare-earth chalcogenides, Yb 6 Ga 4 S 15 and Lu 5 GaS 9 , have been prepared by solid-state reactions of an elemental mixture at high temperatures. Their structures were determined on the basis of single-crystal X-ray diffraction. Yb 6 Ga 4 S 15 crystallizes in the monoclinic space group C2/m (no.12) [a = 23.557(2) Å, b = 3.7664(4) Å, c = 12.466(1) Å, β = 90.915(9)°, V = 1105.9(2) Å 3 and Z = 2], whereas Lu 5 GaS 9 crystallizes in the triclinic space group P1[combining macron] (no.2) [a = 7.735(3) Å, b = 10.033(4) Å, c = 10.120(4) Å, α = 106.296(4)°, β = 100.178(5)°, γ = 101.946(3)°, V = 714.1(5) Å 3 and Z = 2]. Both the structures feature complicated three dimensional frameworks with the unique interlinkages of GaS 4 as basic building units. Significantly, photo-electrochemical measurements indicated that title compounds were photoresponsive under visible-light illumination. Furthermore, the UV-visible-near IR diffuse reflectance spectra, thermal stabilities, electronic structures, physical properties as well as a structure change trend of the ternary rare-earth/gallium/sulfur compounds have been evaluated.

Synthesis, Crystal Chemistry, and Physical Properties of Ternary Intermetallic Compounds An2T2X( An=Pu, Am; X=ln, Sn; T=Co, Ir, Ni, Pd, Pt, Rh)

NASA Astrophysics Data System (ADS)

Pereira, L. C. J.; Wastin, F.; Winand, J. M.; Kanellakopoulos, B.; Rebizant, J.; Spirlet, J. C.; Almeida, M.

1997-11-01

The synthesis, structural, and physical characterization of nine new ternary intermetallic compounds belonging to the isostructural An2T2Xfamily with the transuranium Pu and Am elements, namely, Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, are reported. From these compounds only Pu 2Rh 2In, Am 2Ni 2Sn, and Am 2Pd 2Sn melt incongruently. All of these compounds crystallize in a tetragonal U 3Si 2-type structure, with the space group P4/ mbm, ( Z=2) as most of the U and Np 2-2-1 compounds already found. In this structure, Anatoms occupy the 4 h( x1, x1+0.5, 0.5), Tthe 4 g( x2, x2+0.5, 0), and Xthe 2 a(0, 0, 0) positions. The average values of x1and x2are, respectively, 0.17 and 0.37. Single-crystal X-ray data were refined to R/ RW=0.045/0.066, 0.043/0.072, 0.066/0.080, 0.070/0.098, 0.029/0.048, 0.055/0.080, 0.073/0.096, 0.048/0.086, 0.048/0.065 for Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, respectively, for seven variables. The variation of the lattice parameters and the range of stability of the 2-2-1 phase are discussed in terms of the substitution of different An(actinide), T(transition metal), and X( p-electron) elements in their crystal structure. The possible role of spin fluctuations in the low-temperature behavior of the Pu samples is indicated by magnetic and electrical resistivity measurements.

Color of Minerals. Earth Science Curriculum Project Pamphlet Series PS-6.

ERIC Educational Resources Information Center

Rapp, George, Jr.

The causes for many of the colors exhibited by minerals are presented to students. Several theories of modern physics are introduced. The nature of light, the manner in which light interacts with matter, atomic theory, and crystal structure are all discussed in relation to the origin of color in minerals. Included are color pictures of many…

Predicting Molecular Crystal Properties from First Principles: Finite-Temperature Thermochemistry to NMR Crystallography.

PubMed

Beran, Gregory J O; Hartman, Joshua D; Heit, Yonaton N

2016-11-15

Molecular crystals occur widely in pharmaceuticals, foods, explosives, organic semiconductors, and many other applications. Thanks to substantial progress in electronic structure modeling of molecular crystals, attention is now shifting from basic crystal structure prediction and lattice energy modeling toward the accurate prediction of experimentally observable properties at finite temperatures and pressures. This Account discusses how fragment-based electronic structure methods can be used to model a variety of experimentally relevant molecular crystal properties. First, it describes the coupling of fragment electronic structure models with quasi-harmonic techniques for modeling the thermal expansion of molecular crystals, and what effects this expansion has on thermochemical and mechanical properties. Excellent agreement with experiment is demonstrated for the molar volume, sublimation enthalpy, entropy, and free energy, and the bulk modulus of phase I carbon dioxide when large basis second-order Møller-Plesset perturbation theory (MP2) or coupled cluster theories (CCSD(T)) are used. In addition, physical insight is offered into how neglect of thermal expansion affects these properties. Zero-point vibrational motion leads to an appreciable expansion in the molar volume; in carbon dioxide, it accounts for around 30% of the overall volume expansion between the electronic structure energy minimum and the molar volume at the sublimation point. In addition, because thermal expansion typically weakens the intermolecular interactions, neglecting thermal expansion artificially stabilizes the solid and causes the sublimation enthalpy to be too large at higher temperatures. Thermal expansion also frequently weakens the lower-frequency lattice phonon modes; neglecting thermal expansion causes the entropy of sublimation to be overestimated. Interestingly, the sublimation free energy is less significantly affected by neglecting thermal expansion because the systematic errors in the enthalpy and entropy cancel somewhat. Second, because solid state nuclear magnetic resonance (NMR) plays an increasingly important role in molecular crystal studies, this Account discusses how fragment methods can be used to achieve higher-accuracy chemical shifts in molecular crystals. Whereas widely used plane wave density functional theory models are largely restricted to generalized gradient approximation (GGA) functionals like PBE in practice, fragment methods allow the routine use of hybrid density functionals with only modest increases in computational cost. In extensive molecular crystal benchmarks, hybrid functionals like PBE0 predict chemical shifts with 20-30% higher accuracy than GGAs, particularly for 1 H, 13 C, and 15 N nuclei. Due to their higher sensitivity to polarization effects, 17 O chemical shifts prove slightly harder to predict with fragment methods. Nevertheless, the fragment model results are still competitive with those from GIPAW. The improved accuracy achievable with fragment approaches and hybrid density functionals increases discrimination between different potential assignments of individual shifts or crystal structures, which is critical in NMR crystallography applications. This higher accuracy and greater discrimination are highlighted in application to the solid state NMR of different acetaminophen and testosterone crystal forms.

Single crystal growth, characterization and high-pressure Raman spectroscopy of impurity-free magnesite (MgCO3)

NASA Astrophysics Data System (ADS)

Liang, Wen; Li, Zeming; Yin, Yuan; Li, Rui; Chen, Lin; He, Yu; Dong, Haini; Dai, Lidong; Li, Heping

2018-05-01

The understanding of the physical and chemical properties of magnesite (MgCO3) under deep-mantle conditions is highly important to capture the essence of deep-carbon storage in Earth's interior. To develop standard rating scales, the impurity-free magnesite single crystal, paying particular attention to the case of avoiding adverse impacts of Ca2+, Fe2+, and Mn2+ impurities in natural magnesite, is undoubtedly necessary for all research of magnesite, including crystalline structural phase transitions, anisotropic elasticity and conductivity, and equation of state (EoS). Thus, a high-quality single crystal of impurity-free magnesite was grown successfully for the first time using the self-flux method under high pressure-temperature conditions. The size of the magnesite single crystal, observed in a plane-polarized microscope, exceeds 200 μm, and the crystal exhibits a rhombohedral structure to cleave along the (101) plane. In addition, its composition of Mg0.999 ± 0.001CO3 was quantified through electron probing analysis. The structural property was investigated by means of single crystal X-ray diffraction and the unit cell dimensions obtained in the rhombohedral symmetry of the R\\bar {3}c space group are a = 4.6255 (3) and c = 14.987 (2), and the final R = 0.0243 for 718 reflections. High-pressure Raman spectroscopy of the magnesite single crystal was performed up to 27 GPa at ambient temperature. All Raman active bands, ν i, without any splitting increased almost linearly with increasing pressure. In combination with the high-pressure Raman results {{d/ν _i}}{{{d}P}} and the bulk modulus K T (103 GPa) reported from magnesite EoS studies, the mode Grüneisen parameters (1.49, 1.40, 0.26, and 0.27) of each vibration ( T, L, ν 4, and ν 1) were calculated.

Identification of Gravity-Related Effects on Crystal Growth From Melts With an Immiscibility Gap

NASA Technical Reports Server (NTRS)

Kassemi, M.; Sayir, A.; Farmer, S.

1999-01-01

This work involves an experimental-numerical approach to study the effects of natural and Marangoni convections on solidification of single crystals from a silicate melt with a liquid-liquid immiscibility gap. Industrial use of crystals grown from silicate melts is becoming increasingly important in electronic, optical, and high temperature structural applications. Even the simplest silicate systems like Al203-SiO2 have had, and will continue to have, a significant role in the development of traditional and advanced ceramics. A unique feature of crystals grown from the silicate systems is their outstanding linear electro-optic properties. They also exhibit exceptionally high optical rotativity. As a result, these crystals are attractive materials for dielectric, optical, and microwave applications. Experimental work in our laboratory has indicated that directional solidification of a single crystal mullite appears to be preceded by liquid-liquid phase separation in the melt. Disruption of the immiscible state results in crystallization of a two phase structure. There is also evidence that mixing in the melt caused by density-driven convection can significantly affect the stability of the immiscible liquid layers and result in poly-crystalline growth. On earth, the immiscible state has only been observed for small diameter crystals grown in float zone systems where natural convection is almost negligible. Therefore, it is anticipated that growth of large single crystals from silicate melts would benefit from microgravity conditions because of the reduction of the natural convective mixing. The main objective of this research is to determine the effects of transport processes on the phase separation in the melt during growth of a single crystal while addressing the following issues: (1) When do the immiscible layers form and are they real?; (2) What are the main physical characteristics of the immiscible liquids?; and (3) How mixing by natural or Marangoni convection affects the stability of the phase separated melt.

Ab initio molecular crystal structures, spectra, and phase diagrams.

PubMed

Hirata, So; Gilliard, Kandis; He, Xiao; Li, Jinjin; Sode, Olaseni

2014-09-16

Conspectus Molecular crystals are chemists' solids in the sense that their structures and properties can be understood in terms of those of the constituent molecules merely perturbed by a crystalline environment. They form a large and important class of solids including ices of atmospheric species, drugs, explosives, and even some organic optoelectronic materials and supramolecular assemblies. Recently, surprisingly simple yet extremely efficient, versatile, easily implemented, and systematically accurate electronic structure methods for molecular crystals have been developed. The methods, collectively referred to as the embedded-fragment scheme, divide a crystal into monomers and overlapping dimers and apply modern molecular electronic structure methods and software to these fragments of the crystal that are embedded in a self-consistently determined crystalline electrostatic field. They enable facile applications of accurate but otherwise prohibitively expensive ab initio molecular orbital theories such as Møller-Plesset perturbation and coupled-cluster theories to a broad range of properties of solids such as internal energies, enthalpies, structures, equation of state, phonon dispersion curves and density of states, infrared and Raman spectra (including band intensities and sometimes anharmonic effects), inelastic neutron scattering spectra, heat capacities, Gibbs energies, and phase diagrams, while accounting for many-body electrostatic (namely, induction or polarization) effects as well as two-body exchange and dispersion interactions from first principles. They can fundamentally alter the role of computing in the studies of molecular crystals in the same way ab initio molecular orbital theories have transformed research practices in gas-phase physical chemistry and synthetic chemistry in the last half century. In this Account, after a brief summary of formalisms and algorithms, we discuss applications of these methods performed in our group as compelling illustrations of their unprecedented power in addressing some of the outstanding problems of solid-state chemistry, high-pressure chemistry, or geochemistry. They are the structure and spectra of ice Ih, in particular, the origin of two peaks in the hydrogen-bond-stretching region of its inelastic neutron scattering spectra, a solid-solid phase transition from CO2-I to elusive, metastable CO2-III, pressure tuning of Fermi resonance in solid CO2, and the structure and spectra of solid formic acid, all at the level of second-order Møller-Plesset perturbation theory or higher.

Flow induced/ refined solution crystallization of a semiconducting polymer

NASA Astrophysics Data System (ADS)

Nguyen, Ngoc A.

Organic photovoltaics, a new generation of solar cells, has gained scientific and economic interests due to the ability of solution-processing and potentially low-cost power production. Though, the low power conversion efficiency of organic/ plastic solar cells is one of the most pertinent challenges that has appealed to research communities from many different fields including materials science and engineering, electrical engineering, chemical engineering, physics and chemistry. This thesis focuses on investigating and controlling the morphology of a semi-conducting, semi-crystalline polymer formed under shear-flow. Molecular structures and processing techniques are critical factors that significantly affect the morphology formation in the plastic solar cells, thus influencing device performance. In this study, flow-induced solution crystallization of poly (3-hexylthiophene) (P3HT) in a poor solvent, 2-ethylnapthalene (2-EN) was utilized to make a paint-like, structural liquid. The polymer crystals observed in this structured paint are micrometers long, nanometers in cross section and have a structure similar to that formed under quiescent conditions. There is pi-pi stacking order along the fibril axis, while polymer chain folding occurs along the fibril width and the order of the side-chain stacking is along fibril height. It was revealed that shear-flow not only induces P3HT crystallization from solution, but also refines and perfects the P3HT crystals. Thus, a general strategy to refine the semiconducting polymer crystals from solution under shear-flow has been developed and employed by simply tuning the processing (shearing) conditions with respect to the dissolution temperature of P3HT in 2-EN. The experimental results demonstrated that shear removes defects and allows more perfect crystals to be formed. There is no glass transition temperature observed in the crystals formed using the flow-induced crystallization indicating a significantly different morphology formation in comparison to that of the pristine (as-received) P3HT. As a result, single P3HT crystals with high surface energy chain folds were analyzed and determined. Previous reported results of infinite melting enthalpy of extended chain P3HT crystals are much higher than the result discovered in this study. The findings in this study revealed that the infinite melting enthalpy of chain-folded P3HT crystals is considerably decreased due to the presence of this P3HT chain-folded surface energy. In this study, the kinetics and mechanism of P3HT crystallization under shear-flow was thoroughly investigated as well. A homogeneous nucleation of P3HT was observed that allows one dimensional fibril crystal growth. The micrometer long P3HT crystals are formed and limited by the contact time between the P3HT molecules. Furthermore, it was found that phenyl-C61-butyric acid methyl ester (PCBM) nanoparticles inhibit the crystallization of P3HT under shear. However, the shear-flow leads to nanophase agglomeration of PCBM and creates percolation of P3HT fibril crystal networks and the PCBM phase separated domains that apparently present better pathways for transporting electrons and holes. Interestingly, the structured liquid was simply applied onto substrates with a paintbrush resulting in similar device performance to those made with current techniques in which the morphology is commonly formed during application or post-processing steps. These detailed findings are given and discussed in the thesis.

Solution-grown crystals for neutron radiation detectors, and methods of solution growth

DOEpatents

Zaitseva, Natalia P; Hull, Giulia; Cherepy, Nerine J; Payne, Stephen A; Stoeffl, Wolfgang

2012-06-26

A method according to one embodiment includes growing an organic crystal from solution, the organic crystal exhibiting a signal response signature for neutrons from a radioactive source. A system according to one embodiment includes an organic crystal having physical characteristics of formation from solution, the organic crystal exhibiting a signal response signature for neutrons from a radioactive source; and a photodetector for detecting the signal response of the organic crystal. A method according to another embodiment includes growing an organic crystal from solution, the organic crystal being large enough to exhibit a detectable signal response signature for neutrons from a radioactive source. An organic crystal according to another embodiment includes an organic crystal having physical characteristics of formation from solution, the organic crystal exhibiting a signal response signature for neutrons from a radioactive source, wherein the organic crystal has a length of greater than about 1 mm in one dimension.

A Physical Chemistry Experiment in Polymer Crystallization Kinetics

ERIC Educational Resources Information Center

Singfield, Kathy L.; Chisholm, Roderick A.; King, Thomas L.

2012-01-01

A laboratory experiment currently used in an undergraduate physical chemistry lab to investigate the rates of crystallization of a polymer is described. Specifically, the radial growth rates of typical disc-shaped crystals, called spherulites, growing between microscope glass slides are measured and the data are treated according to polymer…

Crystal engineering of giant molecules based on perylene diimide conjugated polyhedral oligomeric silsesquioxane nano-atom

NASA Astrophysics Data System (ADS)

Ren, He

Molecular architectures and topologies are found contributing to the formation of supramolecular structures of giant molecules. Dr. Cheng's research group developed a diverse of giant molecules via precisely controlled chemistry synthetic routes. These giant molecules can be categorized into several different families, namely giant surfactants, giant shape amphiphiles and giant polyhedron. By analyzing the hierarchical structures of these carefully designed and precisely synthesized giant molecules, the structural factors which affect, or even dominates, in some cases, the formation of supramolecular structures are revealed in these intensive researches. The results will further contribute to the understanding of dependence of supramolecular structures on molecular designs as well as molecular topology, and providing a practical solution to the scaling up of microscopic molecular functionalities to macroscopic material properties. Molecular Nano Particles (MNPs), including fullerene (C60), POSS, Polyoxometalate (POM) and proteins etc., is defined and applied as a specific type of building blocks in the design and synthesis of giant molecules. The persistence in shape and symmetry is considered as one of the major properties of MNPs. This persistence will support the construction of giant molecules for further supramolecular structures' study by introducing specific shapes, or precisely located side groups which will facilitate self-assembling behaviors with pre-programmed secondary interactions. Dictating material physical properties by its chemical composition is an attractive yet currently failed approach in the study of materials. However, the pursuit of determining material properties by microscopic molecular level properties is never seized, and found its solution when the idea of crystal engineering is raised: should each atom in the material is located exactly where it is designed to be and is properly bonded, the property of the material is hence determined. In such "bottom-up" approach, the precise fabrication of 2 nm 100 nm nanostructures, is of great research interest. In this thesis, crystal engineering of giant molecules based on PDI conjugated POSS Nano-Atom (PDI-BPOSS) nano-atoms via self-assembly is performed and studied. Herein, three different giant molecules were synthesized: shape amphiphile, m-phenyl-(PDI-BPOSS)2 (S1) and tetrahedron, R-(PDI-BPOSS)4 (S2) and S-(PDI-BPOSS)4 (S3). Single crystals were grown for S1 and S2, X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and transmission electron microscopy (TEM) were performed, and crystal structures of these samples were determined, while hexagonal superlattice without crystal order can be observed for S3 to exhibit crystal-like morphology.

Structures and properties of materials recovered from high shock pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nellis, W.J.

1994-03-01

Shock compression produces high dynamic pressures, densities, temperatures, and their quench rates. Because of these extreme conditions, shock compression produces materials with novel crystal structures, microstructures, and physical properties. Using a 6.5-m-long two-stage gun, we perform experiments with specimens up to 10 mm in diameter and 0.001--1 mm thick. For example, oriented disks of melt-textured superconducting YBa{sub 2}Cu{sub 3}O{sub 7} were shocked to 7 GPa without macroscopic fracture. Lattice defects are deposited in the crystal, which improve magnetic hysteresis at {approximately}1 kOe. A computer code has been developed to simulate shock compaction of 100 powder particles. Computations will be comparedmore » with experiments with 15--20 {mu}m Cu powders. The method is applicable to other powders and dynamic conditions.« less

Circularly polarized Raman study on diamond structure crystals

NASA Astrophysics Data System (ADS)

Lee, Je-Ho; Kim, Sera; Seong, Maeng-Je

2018-01-01

Circularly polarized Raman and/or photoluminescence (PL) analyses have recently been very important in studying physical properties of many layered materials that were either mechanically exfoliated or grown by chemical-vapor-deposition (CVD) on silicon substrates. Since silicon Raman signal is always accompanied by the circularly polarized Raman and/or PL signal from the layered materials, observation of proper circularly polarized Raman selection rules on silicon substrates would be extremely good indicator that the circularly polarized Raman and/or PL measurements on the layered materials were done properly. We have performed circularly polarized Raman measurements on silicon substrates and compared the results with the Raman intensities calculated by using Raman tensors of the diamond crystal structure. Our experimental results were in excellent agreement with the calculation. Similar circularly polarized Raman analysis done on germanium substrate also showed good agreement.

Widely tunable band gap in a multivalley semiconductor SnSe by potassium doping

NASA Astrophysics Data System (ADS)

Zhang, Kenan; Deng, Ke; Li, Jiaheng; Zhang, Haoxiong; Yao, Wei; Denlinger, Jonathan; Wu, Yang; Duan, Wenhui; Zhou, Shuyun

2018-05-01

SnSe, a group IV-VI monochalcogenide with layered crystal structure similar to black phosphorus, has recently attracted extensive interest due to its excellent thermoelectric properties and potential device applications. Experimental electronic structure of both the valence and conduction bands is critical for understanding the effects of hole versus electron doping on the thermoelectric properties, and to further reveal possible change of the band gap upon doping. Here, we report the multivalley valence bands with a large effective mass on semiconducting SnSe crystals and reveal single-valley conduction bands through electron doping to provide a complete picture of the thermoelectric physics. Moreover, by electron doping through potassium deposition, the band gap of SnSe can be widely tuned from 1.2 eV to 0.4 eV, providing new opportunities for tunable electronic and optoelectronic devices.

Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

DOEpatents

Sachtler, W.M.H.; Huang, Y.Y.

1998-07-28

Methods are disclosed for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physical sorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics. 17 figs.

Optical, Structural, and Thermal Properties of Cerium-Doped Zinc Borophosphate Glasses.

PubMed

Choi, Su-Yeon; Ryu, Bong-Ki

2015-11-01

In this study, we verify the relationship between the optical properties and structure of cerium-doped zinc borophosphate glasses that have concurrence of non-bridging oxygen (NBO) and bridging oxygen (BO), Ce3+ and Ce4+, and BO3 structure and BO4 structure. We prepared cerium-doped zinc borophosphate glass with various compositions, given by xCeO2-(100-x)[50ZnO-10B2O3 -40P2O5] (x = 1 mol% to 6 mol%), and analyzed their optical band energy, glass transition temperature, crystallization temperature, density, and molar volume. Some of the techniques used for analysis were Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). In the investigated glasses, the optical band gap energy decreased from 3.28 eV to 1.73 eV. From these results, we can deduce the changes when transitions occur from BO to NBO, from Ce3+ to Ce4+, and from the BO3 structure to the BO4 structure with increasing CeO2 content using FT-IR and XPS analysis. We also verified the changes in structural and physical properties from quantitative properties such as glass transition temperature, crystallization temperature, density, and molar volume.

Therapeutic Antibody Engineering To Improve Viscosity and Phase Separation Guided by Crystal Structure.

PubMed

Chow, Chi-Kin; Allan, Barrett W; Chai, Qing; Atwell, Shane; Lu, Jirong

2016-03-07

Antibodies at high concentrations often reveal unanticipated biophysical properties suboptimal for therapeutic development. The purpose of this work was to explore the use of point mutations based on crystal structure information to improve antibody physical properties such as viscosity and phase separation (LLPS) at high concentrations. An IgG4 monoclonal antibody (Mab4) that exhibited high viscosity and phase separation at high concentration was used as a model system. Guided by the crystal structure, four CDR point mutants were made to evaluate the role of hydrophobic and charge interactions on solution behavior. Surprisingly and unpredictably, two of the charge mutants, R33G and N35E, showed a reduction in viscosity and a lower propensity to form LLPS at high concentration compared to the wild-type (WT), while a third charge mutant S28K showed an increased propensity to form LLPS compared to the WT. A fourth mutant, F102H, had reduced hydrophobicity, but unchanged viscosity and phase separation behavior. We further evaluated the correlation of various biophysical measurements including second virial coefficient (A2), interaction parameter (kD), weight-average molecular weight (WAMW), and hydrodynamic diameters (DH), at relatively low protein concentration (4 to 15 mg/mL) to physical properties, such as viscosity and liquid-liquid phase separation (LLPS), at high concentration. Surprisingly, kD measured using dynamic light scattering (DLS) at low antibody concentration correlated better with viscosity and phase separation than did A2 for Mab4. Our results suggest that the high viscosity and phase separation observed at high concentration for Mab4 are mainly driven by charge and not hydrophobicity.

The Physics of Hard Spheres Experiment on MSL-1: Required Measurements and Instrument Performance

NASA Technical Reports Server (NTRS)

Doherty, Michael P.; Lant, Christian T.; Ling, Jerri S.

1998-01-01

The Physics of HArd Spheres Experiment (PHaSE), one of NASA Lewis Research Center's first major light scattering experiments for microgravity research on complex fluids, flew on board the Space Shuttle's Microgravity Science Laboratory (MSL-1) in 1997. Using colloidal systems of various concentrations of micron-sized plastic spheres in a refractive index-matching fluid as test samples, illuminated by laser light during and after crystallization, investigations were conducted to measure the nucleation and growth rate of colloidal crystals as well as the structure, rheology, and dynamics of the equilibrium crystal. Together, these measurements support an enhanced understanding of the nature of the liquid-to-solid transition. Achievement of the science objectives required an accurate experimental determination of eight fundamental properties for the hard sphere colloidal samples. The instrument design met almost all of the original measurement requirements, but with compromise on the number of samples on which data were taken. The instrument performs 2-D Bragg and low angle scattering from 0.4 deg. to 60 deg., dynamic and single-channel static scattering from 10 deg. to 170 deg., rheology using fiber optics, and white light imaging of the sample. As a result, PHaSE provided a timely microgravity demonstration of critical light scattering measurement techniques and hardware concepts, while generating data already showing promise of interesting new scientific findings in the field of condensed matter physics.

Elasticity and dislocation anelasticity of crystals

NASA Astrophysics Data System (ADS)

Nikanorov, S. P.; Kardashev, B. K.

The book is concerned with the application of the results of physical acoustic studies of elasticity and dislocation anelasticity to the investigation of interatomic interactions and interactions between lattice defects. The analysis of the potential functions determining the energy of interatomic interactions is based on a study of the elastic properties of crystals over a wide temperature range; data on the dislocation structure and on the interaction between dislocations and point defects are based mainly on a study of inelastic effects. Particular attention is given to the relationship between microplastic effects and the initial stage of plastic deformation under conditions of elastic oscillations, when the multiplication of dislocations is negligible.

Pharmaceutical Cocrystals and Their Physicochemical Properties

PubMed Central

2009-01-01

Over the last 20 years, the number of publications outlining the advances in design strategies, growing techniques, and characterization of cocrystals has continued to increase significantly within the crystal engineering field. However, only within the last decade have cocrystals found their place in pharmaceuticals, primarily due to their ability to alter physicochemical properties without compromising the structural integrity of the active pharmaceutical ingredient (API) and thus, possibly, the bioactivity. This review article will highlight and discuss the advances made over the last 10 years pertaining to physical and chemical property improvements through pharmaceutical cocrystalline materials and, hopefully, draw closer the fields of crystal engineering and pharmaceutical sciences. PMID:19503732

A Reproducible Approach of Preparing High-Quality Overdoped Bi 2 Sr 2 CaCu 2 O 8+δ Single Crystals by Oxygen Annealing and Quenching Method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yu-Xiao; Zhao, Lin; Gu, Gen-Da

2016-06-01

Here, we report a reproducible approach in preparing high-quality overdoped Bi 2Sr 2 CaCu 2 O 8+δ (Bi2212) single crystals by annealing Bi2212 crystals in high oxygen pressure followed by a fast quenching. High-quality overdoped and heavily overdoped Bi2212 single crystals are obtained by controlling the annealing oxygen pressure. Furthermore, we find that, beyond a limit of oxygen pressure that can achieve most heavily overdoped Bi2212 with a T c ~63 K, the annealed Bi2212 begins to decompose. This accounts for the existence of the hole-doping limit and thus the T c limit in the heavily overdoped region of Bi2212more » by the oxygen annealing process. Our results provide a reliable way in preparing high-quality overdoped and heavily overdoped Bi2212 crystals that are important for studies of the physical properties, electronic structure and superconductivity mechanism of the cuprate superconductors.« less

A model for finite-deformation nonlinear thermomechanical response of single crystal copper under shock conditions

NASA Astrophysics Data System (ADS)

Luscher, Darby J.; Bronkhorst, Curt A.; Alleman, Coleman N.; Addessio, Francis L.

2013-09-01

A physically consistent framework for combining pressure-volume-temperature equations of state with crystal plasticity models is developed for the application of modeling the response of single and polycrystals under shock conditions. The particular model is developed for copper, thus the approach focuses on crystals of cubic symmetry although many of the concepts in the approach are applicable to crystals of lower symmetry. We employ a multiplicative decomposition of the deformation gradient into isochoric elastic, thermoelastic dilation, and plastic parts leading to a definition of isochoric elastic Green-Lagrange strain. This finite deformation kinematic decomposition enables a decomposition of Helmholtz free-energy into terms reflecting dilatational thermoelasticity, strain energy due to long-range isochoric elastic deformation of the lattice and a term reflecting energy stored in short range elastic lattice deformation due to evolving defect structures. A model for the single crystal response of copper is implemented consistent with the framework into a three-dimensional Lagrangian finite element code. Simulations exhibit favorable agreement with single and bicrystal experimental data for shock pressures ranging from 3 to 110 GPa.

229Thorium-doped calcium fluoride for nuclear laser spectroscopy.

PubMed

Dessovic, P; Mohn, P; Jackson, R A; Winkler, G; Schreitl, M; Kazakov, G; Schumm, T

2014-03-12

The (229)thorium isotope presents an extremely low-energy isomer state of the nucleus which is expected around 7.8 eV, in the vacuum ultraviolet (VUV) regime. This unique system may bridge between atomic and nuclear physics, enabling coherent manipulation and precision spectroscopy of nuclear quantum states using laser light. It has been proposed to implant (229)thorium into VUV transparent crystal matrices to facilitate laser spectroscopy and possibly realize a solid-state nuclear clock. In this work, we validate the feasibility of this approach by computer modelling of thorium doping into calcium fluoride single crystals. Using atomistic modelling and full electronic structure calculations, we find a persistent large band gap and no additional electronic levels emerging in the middle of the gap due to the presence of the dopant, which should allow direct optical interrogation of the nuclear transition.Based on the electronic structure, we estimate the thorium nuclear quantum levels within the solid-state environment. Precision laser spectroscopy of these levels will allow the study of a broad range of crystal field effects, transferring Mössbauer spectroscopy into the optical regime.

New mixed ligand cobalt(II/III) complexes based on the drug sodium valproate and bioactive nitrogen-donor ligands. Synthesis, structure and biological properties

NASA Astrophysics Data System (ADS)

Abu Ali, Hijazi; Abu Shamma, Amani; Kamel, Shayma

2017-08-01

New cobalt valproate complexes with different nitrogen based ligands were synthesized and characterized using various techniques such as IR, UV-Vis, single crystal X-ray diffraction as well as other physical properties. The general formula of the prepared complexes is [Con(valp)m(L)z], (n = 1, 2 …; m = 1, 2, …; Z = 1, 2 …). The complexes [Co2(valp)4] (1), [Co(valp)2(2-ampy)2] (2) and [Co2(valp)4(quin)2] (3) showed different carboxylate coordination modes. The crystal structures of the complexes 2 and 3 were determined using single crystal X-ray diffraction. Kinetic studies of hydrolysis reactions of BNPP [bis-(p-nitrophenyl)phosphate] with complexes 2 and 3 were performed. The hydrolysis rate of BNPP was studied at different temperatures, pH and concentrations by UV-Vis spectrophotometric method. The results showed that the hydrolysis rate of BNPP was 7.70 × 102 L mol-1 s-1 for (3) and 2.60 × 10-1 L mol-1 s-1 for (2).

Ti, Ni and TiNi nanoparticles physically synthesized by Ar+ beam milling.

PubMed

Torres Castro, A; López Cuéllar, E; José Yacamán, M; Ortiz Méndez, U

2008-12-01

When the size of a particle decreases around 100 nm or less, there is a change in properties from those shown in the bulk material. In this work approximately 3 nm nanoparticles of Ni, Ti and TiNi bimetallic are produced using physical vapor deposition (PVD). Nanoparticles are characterized by High Resolution Transmission Electron Microscopy (HRTEM), High Angle Annular Dark Field (HAADF), Electron Diffraction (ED). The results show that all nanoparticles maintain the same crystal structure of bulk material but a change in their lattice parameter is produced.

The Key Ingredients of the Electronic Structure of FeSe

NASA Astrophysics Data System (ADS)

Coldea, Amalia I.; Watson, Matthew D.

2018-03-01

FeSe is a fascinating superconducting material at the frontier of research in condensed matter physics. Here, we provide an overview of the current understanding of the electronic structure of FeSe, focusing in particular on its low-energy electronic structure as determined from angle-resolved photoemission spectroscopy, quantum oscillations, and magnetotransport measurements of single-crystal samples. We discuss the unique place of FeSe among iron-based superconductors, as it is a multiband system exhibiting strong orbitally dependent electronic correlations and unusually small Fermi surfaces and is prone to different electronic instabilities. We pay particular attention to the evolution of the electronic structure that accompanies the tetragonal-orthorhombic structural distortion of the lattice around 90 K, which stabilizes a unique nematic electronic state. Finally, we discuss how the multiband multiorbital nematic electronic structure impacts our understanding of the superconductivity, and show that the tunability of the nematic state with chemical and physical pressure helps to disentangle the role of different competing interactions relevant for enhancing superconductivity.

High-pressure crystallography of periodic and aperiodic crystals

PubMed Central

Hejny, Clivia; Minkov, Vasily S.

2015-01-01

More than five decades have passed since the first single-crystal X-ray diffraction experiments at high pressure were performed. These studies were applied historically to geochemical processes occurring in the Earth and other planets, but high-pressure crystallography has spread across different fields of science including chemistry, physics, biology, materials science and pharmacy. With each passing year, high-pressure studies have become more precise and comprehensive because of the development of instrumentation and software, and the systems investigated have also become more complicated. Starting with crystals of simple minerals and inorganic compounds, the interests of researchers have shifted to complicated metal–organic frameworks, aperiodic crystals and quasicrystals, molecular crystals, and even proteins and viruses. Inspired by contributions to the microsymposium ‘High-Pressure Crystallography of Periodic and Aperiodic Crystals’ presented at the 23rd IUCr Congress and General Assembly, the authors have tried to summarize certain recent results of single-crystal studies of molecular and aperiodic structures under high pressure. While the selected contributions do not cover the whole spectrum of high-pressure research, they demonstrate the broad diversity of novel and fascinating results and may awaken the reader’s interest in this topic. PMID:25866659

Studying the Impact of Modified Saccharides on the Molecular Dynamics and Crystallization Tendencies of Model API Nifedipine.

PubMed

Kaminska, E; Tarnacka, M; Wlodarczyk, P; Jurkiewicz, K; Kolodziejczyk, K; Dulski, M; Haznar-Garbacz, D; Hawelek, L; Kaminski, K; Wlodarczyk, A; Paluch, M

2015-08-03

Molecular dynamics of pure nifedipine and its solid dispersions with modified carbohydrates as well as the crystallization kinetics of active pharmaceutical ingredient (API) above and below the glass transition temperature were studied in detail by means of broadband dielectric spectroscopy (BDS), differential scanning calorimetry (DSC), and X-ray diffraction method. It was found that the activation barrier of crystallization increases in molecular dispersions composed of acetylated disaccharides, whereas it slightly decreases in those consisting of modified monocarbohydrates for the experiments carried out above the glass transition temperature. As shown by molecular dynamics simulations it can be related to the strength, character, and structure of intermolecular interactions between API and saccharides, which vary dependently on the excipient. Long-term physical stability studies showed that, in solid dispersions consisting of acetylated maltose and acetylated sucrose, the crystallization of nifedipine is dramatically slowed down, although it is still observable for a low concentration of excipients. With increasing content of modified carbohydrates, the crystallization of API becomes completely suppressed. This is most likely due to additional barriers relating to the intermolecular interactions and diffusion of nifedipine that must be overcome to trigger the crystallization process.

Physics of Ultrathin Films and Heterostructures of Rare-Earth Nickelates

DOE PAGES

Middey, Srimanta; Chakhalian, J.; Mahadevan, P.; ...

2016-04-06

The electronic structure of transition metal oxides featuring correlated electrons can be rationalized within the Zaanen-Sawatzky-Allen framework. Following a brief description of the present paradigms of electronic behavior, we focus on the physics of rare-earth nickelates as an archetype of complexity emerging within the charge transfer regime. The intriguing prospect of realizing the physics of high- Tc cuprates through heterostructuring resulted in a massive endeavor to epitaxially stabilize these materials in ultrathin form. A plethora of new phenomena unfolded in such artificial structures due to the effect of epitaxial strain, quantum confinement, and interfacial charge transfer. Here we review themore » present status of artificial rare-earth nickelates in an effort to uncover the interconnection between the electronic and magnetic behavior and the underlying crystal structure. Here, we conclude by discussing future directions to disentangle the puzzle regarding the origin of the metal-insulator transition, the role of oxygen holes, and the true nature of the antiferromagnetic spin configuration in the ultrathin limit.« less

Growth of single-crystalline cobalt silicide nanowires and their field emission property.

PubMed

Lu, Chi-Ming; Hsu, Han-Fu; Lu, Kuo-Chang

2013-07-03

In this work, cobalt silicide nanowires were synthesized by chemical vapor deposition processes on Si (100) substrates with anhydrous cobalt chloride (CoCl2) as precursors. Processing parameters, including the temperature of Si (100) substrates, the gas flow rate, and the pressure of reactions were varied and studied; additionally, the physical properties of the cobalt silicide nanowires were measured. It was found that single-crystal CoSi nanowires were grown at 850°C ~ 880°C and at a lower gas flow rate, while single-crystal Co2Si nanowires were grown at 880°C ~ 900°C. The crystal structure and growth direction were identified, and the growth mechanism was proposed as well. This study with field emission measurements demonstrates that CoSi nanowires are attractive choices for future applications in field emitters.

Optical and Calorimetric Studies of Cholesterol-Rich Filamentous, Helical Ribbon and Crystal Microstructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miroshnikova, Y. A.; Elsenbeck, M.; Zastavker, Y. V.

2009-04-19

Formation of biological self-assemblies at all scales is a focus of studies in fields ranging from biology to physics to biomimetics. Understanding the physico-chemical properties of these self-assemblies may lead to the design of bio-inspired structures and technological applications. Here we examine self-assembled filamentous, helical ribbon, and crystal microstructures formed in chemically defined lipid concentrate (CDLC), a model system for cholesterol crystallization in gallbladder bile. CDLC consists of cholesterol, bilayer-forming amphiphiles, micelle-forming amphiphiles, and water. Phase contrast and differential interference contrast (DIC) microscopy indicate the presence of three microstructure types in all samples studied, and allow for an investigation ofmore » the structures' unique geometries. Additionally, confocal microscopy is used for qualitative assessment of surface and internal composition. To complement optical observations, calorimetric (differential-scanning and modulation) experiments, provide the basis for an in-depth understanding of collective and individual thermal behavior. Observed ''transition'' features indicate clustering and ''straightening'' of helical ribbons into short, increasingly thickening, filaments that dissolve with increasing temperature. These results suggest that all microstructures formed in CDLC may coexist in a metastable chemical equilibrium. Further investigation of the CDLC thermal profile should uncover the process of cholesterol crystallization as well as the unique design and function of microstructures formed in this system.« less

Biomolecular crystals for material applications and a mechanistic study of an iron oxide nanoparticle synthesis

NASA Astrophysics Data System (ADS)

Falkner, Joshua Charles

The three projects within this work address the difficulties of controlling biomolecular crystal formats (i.e. size and shape), producing 3-D ordered composite materials from biomolecular crystal templates, and understanding the mechanism of a practical iron oxide synthesis. The unifying thread consistent throughout these three topics is the development of methods to manipulate nanomaterials using a bottom-up approach. Biomolecular crystals are nanometer to millimeter sized crystals that have well ordered mesoporous solvent channels. The overall physical dimensions of these crystals are highly dependent on crystallization conditions. The controlled growth of micro- and nanoprotein crystals was studied to provide new pathways for creating smaller crystalline protein materials. This method produced tetragonal hen egg-white lysozyme crystals (250--100,000 nm) with near monodisperse size distributions (<15%). With this degree of control, existing protein crystal applications such as drug delivery and analytical sensors can reach their full potential. Applications for larger crystals with inherently ubiquitous pore structures could extend to materials used for membranes or templates. In this work, the porous structure of larger cowpea mosaic virus crystals was used to template metal nanoparticle growth within the body centered cubic crystalline network. The final composite material was found to have long range ordering of palladium and platinum nonocrystal aggregates (10nm) with symmetry consistent to the virus template. Nanoparticle synthesis itself is an immense field of study with an array of diverse applications. The final piece of this work investigates the mechanism behind a previously developed iron oxide synthesis to gain more understanding and direction to future synthesis strategies. The particle growth mechanism was found to proceed by the formation of a solvated iron(III)oleate complex followed by a reduction of iron (III) to iron (II). This unstable iron(II) nucleates to form a wustite (FeO) core which serves as an epitaxial surface for the magnetite (Fe3O4) shell growth. This method produces spherical particles (6-60nm) with relative size distributions of less than 15%.

Bright and durable field-emission source derived from frozen refractory-metal Taylor cones

DOE PAGES

Hirsch, Gregory

2017-02-22

A novel method for creating conical field-emission structures possessing unusual and desirable physical characteristics is described. This process is accomplished by solidification of electrostatically formed high-temperature Taylor cones created on the ends of laser melted refractory-metal wires. Extremely rapid freezing ensures that the resultant solid structures preserve the shape and surface smoothness of the flawless liquid Taylor-cones to a very high degree. The method also enables in situ and rapid restoration of the frozen cones to their initial pristine state after undergoing physical degradation during use. This permits maximum current to be delivered without excessive concern for any associated reductionmore » in field-emitter lifetime resulting from operation near or even above the damage threshold. In addition to the production of field emitters using polycrystalline wires as a substrate, the feasibility of producing monocrystalline frozen Taylor-cones having reproducible crystal orientation by growth on single-crystal wires was demonstrated. Finally, the development of the basic field-emission technology, progress to incorporate it into a pulsed electron gun employing laser-assisted field emission for ultrafast experiments, and some additional advances and opportunities are discussed.« less

Bright and durable field-emission source derived from frozen refractory-metal Taylor cones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hirsch, Gregory

A novel method for creating conical field-emission structures possessing unusual and desirable physical characteristics is described. This process is accomplished by solidification of electrostatically formed high-temperature Taylor cones created on the ends of laser melted refractory-metal wires. Extremely rapid freezing ensures that the resultant solid structures preserve the shape and surface smoothness of the flawless liquid Taylor-cones to a very high degree. The method also enables in situ and rapid restoration of the frozen cones to their initial pristine state after undergoing physical degradation during use. This permits maximum current to be delivered without excessive concern for any associated reductionmore » in field-emitter lifetime resulting from operation near or even above the damage threshold. In addition to the production of field emitters using polycrystalline wires as a substrate, the feasibility of producing monocrystalline frozen Taylor-cones having reproducible crystal orientation by growth on single-crystal wires was demonstrated. Finally, the development of the basic field-emission technology, progress to incorporate it into a pulsed electron gun employing laser-assisted field emission for ultrafast experiments, and some additional advances and opportunities are discussed.« less

Interface dynamics and crystal phase switching in GaAs nanowires

NASA Astrophysics Data System (ADS)

Jacobsson, Daniel; Panciera, Federico; Tersoff, Jerry; Reuter, Mark C.; Lehmann, Sebastian; Hofmann, Stephan; Dick, Kimberly A.; Ross, Frances M.

2016-03-01

Controlled formation of non-equilibrium crystal structures is one of the most important challenges in crystal growth. Catalytically grown nanowires are ideal systems for studying the fundamental physics of phase selection, and could lead to new electronic applications based on the engineering of crystal phases. Here we image gallium arsenide (GaAs) nanowires during growth as they switch between phases as a result of varying growth conditions. We find clear differences between the growth dynamics of the phases, including differences in interface morphology, step flow and catalyst geometry. We explain these differences, and the phase selection, using a model that relates the catalyst volume, the contact angle at the trijunction (the point at which solid, liquid and vapour meet) and the nucleation site of each new layer of GaAs. This model allows us to predict the conditions under which each phase should be observed, and use these predictions to design GaAs heterostructures. These results could apply to phase selection in other nanowire systems.

Interface dynamics and crystal phase switching in GaAs nanowires.

PubMed

Jacobsson, Daniel; Panciera, Federico; Tersoff, Jerry; Reuter, Mark C; Lehmann, Sebastian; Hofmann, Stephan; Dick, Kimberly A; Ross, Frances M

2016-03-17

Controlled formation of non-equilibrium crystal structures is one of the most important challenges in crystal growth. Catalytically grown nanowires are ideal systems for studying the fundamental physics of phase selection, and could lead to new electronic applications based on the engineering of crystal phases. Here we image gallium arsenide (GaAs) nanowires during growth as they switch between phases as a result of varying growth conditions. We find clear differences between the growth dynamics of the phases, including differences in interface morphology, step flow and catalyst geometry. We explain these differences, and the phase selection, using a model that relates the catalyst volume, the contact angle at the trijunction (the point at which solid, liquid and vapour meet) and the nucleation site of each new layer of GaAs. This model allows us to predict the conditions under which each phase should be observed, and use these predictions to design GaAs heterostructures. These results could apply to phase selection in other nanowire systems.

Crystal engineering of novel cocrystals of a triazole drug with 1,4-dicarboxylic acids.

PubMed

Remenar, Julius F; Morissette, Sherry L; Peterson, Matthew L; Moulton, Brian; MacPhee, J Michael; Guzmán, Héctor R; Almarsson, Orn

2003-07-16

Cocrystals of the poorly soluble antifungal drug cis-itraconazole (1) with 1,4-dicarboxylic acids have been prepared. The crystal structure of the succinic acid cocrystal with 1 was determined to be a trimer by single-crystal X-ray. The trimer is comprised of two molecules of 1 oriented in antiparallel fashion to form a pocket with a triazole at either end. The extended succinic acid molecule fills the pocket, bridging the triazole groups through hydrogen-bonding interactions rather than interacting with the more basic piperazine nitrogens. The solubility and dissolution rate of some of the cocrystals are approximately the same as those of the amorphous drug in the commercial formulation and are much higher than those for the crystalline free base. The results suggest that cocrystals of drug molecules have the possibility of achieving the higher oral bioavailability common for amorphous forms of water-insoluble drugs while maintaining the long-term chemical and physical stability that crystal forms provide.

Rotational Symmetry Breaking in a Trigonal Superconductor Nb-doped Bi 2 Se 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asaba, Tomoya; Lawson, B. J.; Tinsman, Colin

2017-01-27

The search for unconventional superconductivity has been focused on materials with strong spin-orbit coupling and unique crystal lattices. Doped bismuth selenide (Bi 2Se 3) is a strong candidate, given the topological insulator nature of the parent compound and its triangular lattice. The coupling between the physical properties in the superconducting state and its underlying crystal symmetry is a crucial test for unconventional superconductivity. In this paper, we report direct evidence that the superconducting magnetic response couples strongly to the underlying trigonal crystal symmetry in the recently discovered superconductor with trigonal crystal structure, niobium (Nb)-doped Bi 2Se 3. As a result,more » the in-plane magnetic torque signal vanishes every 60°. More importantly, the superconducting hysteresis loop amplitude is enhanced along one preferred direction, spontaneously breaking the rotational symmetry. This observation indicates the presence of nematic order in the superconducting ground state of Nb-doped Bi 2Se 3.« less

Physical methods for investigating structural colours in biological systems

PubMed Central

Vukusic, P.; Stavenga, D.G.

2009-01-01

Many biological systems are known to use structural colour effects to generate aspects of their appearance and visibility. The study of these phenomena has informed an eclectic group of fields ranging, for example, from evolutionary processes in behavioural biology to micro-optical devices in technologically engineered systems. However, biological photonic systems are invariably structurally and often compositionally more elaborate than most synthetically fabricated photonic systems. For this reason, an appropriate gamut of physical methods and investigative techniques must be applied correctly so that the systems' photonic behaviour may be appropriately understood. Here, we survey a broad range of the most commonly implemented, successfully used and recently innovated physical methods. We discuss the costs and benefits of various spectrometric methods and instruments, namely scatterometers, microspectrophotometers, fibre-optic-connected photodiode array spectrometers and integrating spheres. We then discuss the role of the materials' refractive index and several of the more commonly used theoretical approaches. Finally, we describe the recent developments in the research field of photonic crystals and the implications for the further study of structural coloration in animals. PMID:19158009

Influence of crystal habit on trimethoprim suspension formulation.

PubMed

Tiwary, A K; Panpalia, G M

1999-02-01

The role of crystal habit in influencing the physical stability and pharmacokinetics of trimethoprim suspensions was examined. Different habits for trimethoprim (TMP) were obtained by recrystallizing the commercial sample (PD) utilizing solvent-change precipitation method. Four distinct habits (microscopic observation) belonging to the same polymorphic state (DSC studies) were selected for studies. Preformulation and formulation studies were carried out on suspension dosage forms containing these crystals. The freshly prepared suspensions were also evaluated for their pharmacokinetic behaviour on healthy human volunteers using a cross over study. Variation of crystallization conditions produces different habits of TMP. Among the different crystal habits exhibiting same polymorphic state, the most anisometric crystal showed best physical stability in terms of sedimentation volume and redispersibility. However, habit did not significantly affect the extent of TMP excreted in urine. Modification of surface morphology without significantly altering the polymorphic state can be utilized for improving physical stability of TMP suspensions. However, the pharmacokinetic profile remains unaltered.

Nematic-like stable glasses without equilibrium liquid crystal phases

DOE Data Explorer

Gomez, Jaritza [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Gujral, Ankit [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Huang, Chengbin [School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA; Bishop, Camille [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Yu, Lian [School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA; Ediger, Mark [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA

2017-02-01

We report the thermal and structural properties of glasses of posaconazole, a rod-like molecule, prepared using physical vapor deposition (PVD). PVD glasses of posaconazole can show substantial molecular orientation depending upon the choice of substrate temperature, Tsubstrate, during deposition.Ellipsometry and IR measurements indicate that glasses prepared at Tsubstrate very near the glass transition temperature (Tg) are highly ordered. For these posaconazole glasses, the orientation order parameter is similar to that observed in macroscopically aligned nematic liquid crystals, indicating that the molecules are mostly parallel to one another and perpendicular to the interface. To our knowledge, these are the most anisotropic glasses ever prepared by PVD from a molecule that does not form equilibrium liquid crystal phases. These results are consistent with a previously proposed mechanism in which molecular orientation in PVD glasses is inherited from the orientation present at the free surface of the equilibrium liquid. This mechanism suggests that molecular orientation at the surface of the equilibrium liquid of posaconazole is nematic-like. Posaconazole glasses can show very high kinetic stability; the isothermal transformation of a 400 nm glass into the supercooled liquid occurs via a propagating front that originates at the free surface and requires ~105 times the structural relaxation time of the liquid (τα). We also studied the kinetic stability of PVD glasses of itraconazole, which is a structurally similar molecule with equilibrium liquid crystal phases. While itraconazole glasses can be even more anisotropic than posaconazole glasses, they exhibit lower kinetic stability.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramadhar, Timothy R.; Zheng, Shao -Liang; Chen, Yu -Sheng

A detailed set of synthetic and crystallographic guidelines for the crystalline sponge method based upon the analysis of expediently synthesized crystal sponges using third-generation synchrotron radiation are reported. The procedure for the synthesis of the zinc-based metal–organic framework used in initial crystal sponge reports has been modified to yield competent crystals in 3 days instead of 2 weeks. These crystal sponges were tested on some small molecules, with two being unexpectedly difficult cases for analysis with in-house diffractometers in regard to data quality and proper space-group determination. These issues were easily resolved by the use of synchrotron radiation using data-collectionmore » times of less than an hour. One of these guests induced a single-crystal-to-single-crystal transformation to create a larger unit cell with over 500 non-H atoms in the asymmetric unit. This led to a non-trivial refinement scenario that afforded the best Flack x absolute stereochemical determination parameter to date for these systems. The structures did not require the use of PLATON/SQUEEZE or other solvent-masking programs, and are the highest-quality crystalline sponge systems reported to date where the results are strongly supported by the data. A set of guidelines for the entire crystallographic process were developed through these studies. In particular, the refinement guidelines include strategies to refine the host framework, locate guests and determine occupancies, discussion of the proper use of geometric and anisotropic displacement parameter restraints and constraints, and whether to perform solvent squeezing/masking. The single-crystal-to-single-crystal transformation process for the crystal sponges is also discussed. The presented general guidelines will be invaluable for researchers interested in using the crystalline sponge method at in-house diffraction or synchrotron facilities, will facilitate the collection and analysis of reliable high-quality data, and will allow construction of chemically and physically sensible models for guest structural determination.« less

Analysis of rapidly synthesized guest-filled porous complexes with synchrotron radiation: Practical guidelines for the crystalline sponge method

DOE PAGES

Ramadhar, Timothy R.; Zheng, Shao -Liang; Chen, Yu -Sheng; ...

2015-01-01

A detailed set of synthetic and crystallographic guidelines for the crystalline sponge method based upon the analysis of expediently synthesized crystal sponges using third-generation synchrotron radiation are reported. The procedure for the synthesis of the zinc-based metal–organic framework used in initial crystal sponge reports has been modified to yield competent crystals in 3 days instead of 2 weeks. These crystal sponges were tested on some small molecules, with two being unexpectedly difficult cases for analysis with in-house diffractometers in regard to data quality and proper space-group determination. These issues were easily resolved by the use of synchrotron radiation using data-collectionmore » times of less than an hour. One of these guests induced a single-crystal-to-single-crystal transformation to create a larger unit cell with over 500 non-H atoms in the asymmetric unit. This led to a non-trivial refinement scenario that afforded the best Flack x absolute stereochemical determination parameter to date for these systems. The structures did not require the use of PLATON/SQUEEZE or other solvent-masking programs, and are the highest-quality crystalline sponge systems reported to date where the results are strongly supported by the data. A set of guidelines for the entire crystallographic process were developed through these studies. In particular, the refinement guidelines include strategies to refine the host framework, locate guests and determine occupancies, discussion of the proper use of geometric and anisotropic displacement parameter restraints and constraints, and whether to perform solvent squeezing/masking. The single-crystal-to-single-crystal transformation process for the crystal sponges is also discussed. The presented general guidelines will be invaluable for researchers interested in using the crystalline sponge method at in-house diffraction or synchrotron facilities, will facilitate the collection and analysis of reliable high-quality data, and will allow construction of chemically and physically sensible models for guest structural determination.« less

Some physical investigations on ZnS 1- xSe x films obtained by selenization of ZnS sprayed films using the Boubaker polynomials expansion scheme

NASA Astrophysics Data System (ADS)

Fridjine, S.; Touihri, S.; Boubaker, K.; Amlouk, M.

2010-01-01

ZnS 1- xSe x thin films have been grown by selenization process, applied to ZnS sprayed thin films deposited on Pyrex glass substrates at 550 °C. The crystal structure and surface morphology were investigated by the XRD technique and by the atomic force microscopy. This structural study shows that selenium-free ( x=0) ZnS thin films, prepared at substrate temperature TS=450 °C, were well crystallized in cubic structure and oriented preferentially along (1 1 1) direction. The thermal and mechanical properties were also investigated using a photothermal protocol along with Vickers hardness measurements. On the other hand, the analyze of the transmittance T( λ) and the reflectance R( λ), optical measurements of these films depicts a decrease in the band gap energy value Eg with an increase in Se content ( x). Indeed, Eg values vary from 3.6 to 3.1 eV.

Structural basis for DNA binding by replication initiator Mcm10

DOE Office of Scientific and Technical Information (OSTI.GOV)

Warren, Eric M.; Vaithiyalingam, Sivaraja; Haworth, Justin

2009-06-30

Mcm10 is an essential eukaryotic DNA replication protein required for assembly and progression of the replication fork. The highly conserved internal domain (Mcm10-ID) has been shown to physically interact with single-stranded (ss) DNA, DNA polymerase alpha, and proliferating cell nuclear antigen (PCNA). The crystal structure of Xenopus laevis Mcm10-ID presented here reveals a DNA binding architecture composed of an oligonucleotide/oligosaccharide-fold followed in tandem by a variant and highly basic zinc finger. NMR chemical shift perturbation and mutational studies of DNA binding activity in vitro reveal how Mcm10 uses this unique surface to engage ssDNA. Corresponding mutations in Saccharomyces cerevisiae resultmore » in increased sensitivity to replication stress, demonstrating the functional importance of DNA binding by this region of Mcm10 to replication. In addition, mapping Mcm10 mutations known to disrupt PCNA, polymerase alpha, and DNA interactions onto the crystal structure provides insight into how Mcm10 might coordinate protein and DNA binding within the replisome.« less

Elastic dependence of defect modes in one-dimensional photonic crystals with a cholesteric elastomer slab

NASA Astrophysics Data System (ADS)

Avendanño, Carlos G.; Martínez, Daniel

2018-07-01

We studied the transmission spectra in a one-dimensional dielectric multilayer photonic structure containing a cholesteric liquid crystal elastomer layer as a defect. For circularly polarized incident electromagnetic waves, we analyzed the optical defect modes induced in the band gap spectrum as a function of the incident angle and the axial strain applied along the same axis as the periodic medium. The physical parameters of the structure were chosen in such a way the photonic band gap of the cholesteric elastomer lies inside that of the multilayer. We found that, in addition to the defect modes associated with the thickness of the defect layer and the anisotropy of the elastic polymer, two new defect modes appear at both band edges of the cholesteric structure, whose amplitudes and spectral positions can be elastically tuned. Particularly, we showed that, at normal incidence, the defect modes shift toward the long-wavelength region with the strain; whereas, for constant elongation, such defects move toward larger frequencies with the incidence angle.

Controlling circular polarization of light emitted by quantum dots using chiral photonic crystal slabs

NASA Astrophysics Data System (ADS)

Lobanov, S. V.; Tikhodeev, S. G.; Gippius, N. A.; Maksimov, A. A.; Filatov, E. V.; Tartakovskii, I. I.; Kulakovskii, V. D.; Weiss, T.; Schneider, C.; Geßler, J.; Kamp, M.; Höfling, S.

2015-11-01

We study the polarization properties of light emitted by quantum dots that are embedded in chiral photonic crystal structures made of achiral planar GaAs waveguides. A modification of the electromagnetic mode structure due to the chiral grating fabricated by partial etching of the waveguide layer has been shown to result in a high circular polarization degree ρc of the quantum dot emission in the absence of external magnetic field. The physical nature of the phenomenon can be understood in terms of the reciprocity principle taking into account the structural symmetry. At the resonance wavelength, the magnitude of | ρc| is predicted to exceed 98%. The experimentally achieved value of | ρc|=81 % is smaller, which is due to the contribution of unpolarized light scattered by grating defects, thus breaking its periodicity. The achieved polarization degree estimated removing the unpolarized nonresonant background from the emission spectra can be estimated to be as high as 96%, close to the theoretical prediction.

Nonequilibrium fluctuations in metaphase spindles: polarized light microscopy, image registration, and correlation functions

NASA Astrophysics Data System (ADS)

Brugués, Jan; Needleman, Daniel J.

2010-02-01

Metaphase spindles are highly dynamic, nonequilibrium, steady-state structures. We study the internal fluctuations of spindles by computing spatio-temporal correlation functions of movies obtained from quantitative polarized light microscopy. These correlation functions are only physically meaningful if corrections are made for the net motion of the spindle. We describe our image registration algorithm in detail and we explore its robustness. Finally, we discuss the expression used for the estimation of the correlation function in terms of the nematic order of the microtubules which make up the spindle. Ultimately, studying the form of these correlation functions will provide a quantitative test of the validity of coarse-grained models of spindle structure inspired from liquid crystal physics.

Charge transport through one-dimensional Moiré crystals

PubMed Central

Bonnet, Roméo; Lherbier, Aurélien; Barraud, Clément; Rocca, Maria Luisa Della; Lafarge, Philippe; Charlier, Jean-Christophe

2016-01-01

Moiré superlattices were generated in two-dimensional (2D) van der Waals heterostructures and have revealed intriguing electronic structures. The appearance of mini-Dirac cones within the conduction and valence bands of graphene is one of the most striking among the new quantum features. A Moiré superstructure emerges when at least two periodic sub-structures superimpose. 2D Moiré patterns have been particularly investigated in stacked hexagonal 2D atomic lattices like twisted graphene layers and graphene deposited on hexagonal boron-nitride. In this letter, we report both experimentally and theoretically evidence of superlattices physics in transport properties of one-dimensional (1D) Moiré crystals. Rolling-up few layers of graphene to form a multiwall carbon nanotube adds boundaries conditions that can be translated into interference fringes-like Moiré patterns along the circumference of the cylinder. Such a 1D Moiré crystal exhibits a complex 1D multiple bands structure with clear and robust interband quantum transitions due to the presence of mini-Dirac points and pseudo-gaps. Our devices consist in a very large diameter (>80 nm) multiwall carbon nanotubes of high quality, electrically connected by metallic electrodes acting as charge reservoirs. Conductance measurements reveal the presence of van Hove singularities assigned to 1D Moiré superlattice effect and illustrated by electronic structure calculations. PMID:26786067

Water polygons in high-resolution protein crystal structures.

PubMed

Lee, Jonas; Kim, Sung-Hou

2009-07-01

We have analyzed the interstitial water (ISW) structures in 1500 protein crystal structures deposited in the Protein Data Bank that have greater than 1.5 A resolution with less than 90% sequence similarity with each other. We observed varieties of polygonal water structures composed of three to eight water molecules. These polygons may represent the time- and space-averaged structures of "stable" water oligomers present in liquid water, and their presence as well as relative population may be relevant in understanding physical properties of liquid water at a given temperature. On an average, 13% of ISWs are localized enough to be visible by X-ray diffraction. Of those, averages of 78% are water molecules in the first water layer on the protein surface. Of the localized ISWs beyond the first layer, almost half of them form water polygons such as trigons, tetragons, as well as expected pentagons, hexagons, higher polygons, partial dodecahedrons, and disordered networks. Most of the octagons and nanogons are formed by fusion of smaller polygons. The trigons are most commonly observed. We suggest that our observation provides an experimental basis for including these water polygon structures in correlating and predicting various water properties in liquid state.

Water polygons in high-resolution protein crystal structures

PubMed Central

Lee, Jonas; Kim, Sung-Hou

2009-01-01

We have analyzed the interstitial water (ISW) structures in 1500 protein crystal structures deposited in the Protein Data Bank that have greater than 1.5 Å resolution with less than 90% sequence similarity with each other. We observed varieties of polygonal water structures composed of three to eight water molecules. These polygons may represent the time- and space-averaged structures of “stable” water oligomers present in liquid water, and their presence as well as relative population may be relevant in understanding physical properties of liquid water at a given temperature. On an average, 13% of ISWs are localized enough to be visible by X-ray diffraction. Of those, averages of 78% are water molecules in the first water layer on the protein surface. Of the localized ISWs beyond the first layer, almost half of them form water polygons such as trigons, tetragons, as well as expected pentagons, hexagons, higher polygons, partial dodecahedrons, and disordered networks. Most of the octagons and nanogons are formed by fusion of smaller polygons. The trigons are most commonly observed. We suggest that our observation provides an experimental basis for including these water polygon structures in correlating and predicting various water properties in liquid state. PMID:19551896

Machine learning for the structure–energy–property landscapes of molecular crystals† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc04665k

PubMed Central

Yang, Jack; Campbell, Joshua E.; Day, Graeme M.; Ceriotti, Michele

2017-01-01

Molecular crystals play an important role in several fields of science and technology. They frequently crystallize in different polymorphs with substantially different physical properties. To help guide the synthesis of candidate materials, atomic-scale modelling can be used to enumerate the stable polymorphs and to predict their properties, as well as to propose heuristic rules to rationalize the correlations between crystal structure and materials properties. Here we show how a recently-developed machine-learning (ML) framework can be used to achieve inexpensive and accurate predictions of the stability and properties of polymorphs, and a data-driven classification that is less biased and more flexible than typical heuristic rules. We discuss, as examples, the lattice energy and property landscapes of pentacene and two azapentacene isomers that are of interest as organic semiconductor materials. We show that we can estimate force field or DFT lattice energies with sub-kJ mol–1 accuracy, using only a few hundred reference configurations, and reduce by a factor of ten the computational effort needed to predict charge mobility in the crystal structures. The automatic structural classification of the polymorphs reveals a more detailed picture of molecular packing than that provided by conventional heuristics, and helps disentangle the role of hydrogen bonded and π-stacking interactions in determining molecular self-assembly. This observation demonstrates that ML is not just a black-box scheme to interpolate between reference calculations, but can also be used as a tool to gain intuitive insights into structure–property relations in molecular crystal engineering. PMID:29675175

X-ray scattering data and structural genomics

NASA Astrophysics Data System (ADS)

Doniach, Sebastian

2003-03-01

High throughput structural genomics has the ambitious goal of determining the structure of all, or a very large number of protein folds using the high-resolution techniques of protein crystallography and NMR. However, the program is facing significant bottlenecks in reaching this goal, which include problems of protein expression and crystallization. In this talk, some preliminary results on how the low-resolution technique of small-angle X-ray solution scattering (SAXS) can help ameliorate some of these bottlenecks will be presented. One of the most significant bottlenecks arises from the difficulty of crystallizing integral membrane proteins, where only a handful of structures are available compared to thousands of structures for soluble proteins. By 3-dimensional reconstruction from SAXS data, the size and shape of detergent-solubilized integral membrane proteins can be characterized. This information can then be used to classify membrane proteins which constitute some 25% of all genomes. SAXS may also be used to study the dependence of interparticle interference scattering on solvent conditions so that regions of the protein solution phase diagram which favor crystallization can be elucidated. As a further application, SAXS may be used to provide physical constraints on computational methods for protein structure prediction based on primary sequence information. This in turn can help in identifying structural homologs of a given protein, which can then give clues to its function. D. Walther, F. Cohen and S. Doniach. "Reconstruction of low resolution three-dimensional density maps from one-dimensional small angle x-ray scattering data for biomolecules." J. Appl. Cryst. 33(2):350-363 (2000). Protein structure prediction constrained by solution X-ray scattering data and structural homology identification Zheng WJ, Doniach S JOURNAL OF MOLECULAR BIOLOGY , v. 316(#1) pp. 173-187 FEB 8, 2002

Structural study and physical properties of a new phosphate KCuFe(PO 4) 2

NASA Astrophysics Data System (ADS)

Badri, Abdessalem; Hidouri, Mourad; López, María Luisa; Pico, Carlos; Wattiaux, Alain; Amara, Mongi Ben

2011-04-01

Single crystals of a new phosphate KCuFe(PO 4) 2 have been prepared by the flux method and its structural and physical properties have been investigated. This compound crystallizes in the monoclinic system with the space group P2 1/ n and its parameters are: a=7.958(3) Å, b=9.931(2) Å, c=9.039(2) Å, β=115.59(3)° and Z=4. Its structure consists of FeO 6 octahedra sharing corners with Cu 2O 8 units of edge-sharing CuO 5 polyhedra to form undulating chains extending infinitely along the b-axis. These chains are connected by the phosphate tetrahedra giving rise to a 3D framework with six-sided tunnels parallel to the [101] direction, where the K + ions are located. The Mössbauer spectroscopy results confirm the exclusive presence of octahedral Fe 3+ ions. The magnetic measurements show the compound to be antiferromagnetic with Cm=5.71 emu K/mol and θ=-156.5 K. The derived experimental effective moment μex=6.76 μB is somewhat higher than the theoretical one of μth=6.16 μB, calculated taking only into account the spin contribution for Fe 3+ and Cu 2+ cations. Electrical measurements allow us to obtain the activation energy (1.22 eV) and the conductivity measurements suggest that the charge carriers through the structure are the potassium cations.

Optimization of the photorefractivity in II-IV semiconductors. Final report, March 1996--March 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jagannathan, G.V.; Trivedi, S.B.; Kutcher, S.W.

1998-11-01

This work was aimed at optimization of the photorefractivity in the II-VI semiconductors CdTe, ZnTe and Cd{sub x{minus}1}Zn{sub (x)}Te for real-time optical signal processing applications at near infrared wavelengths. During this work, several crystals of ZnTe, CdTe and Cd{sub x{minus}1}Zn{sub (x)}Te were grown. Crystal growth of ZnTe and CdTe was carried out using low supersaturation nucleation and `contactless` growth by Vertical Physical Vapor Transport (PVT) in closed ampoules and the CdTe and Cd{sub x{minus}1}Zn{sub (x)}Te crystals were grown using the vertical Bridgman technique. The quality of the crystals grown during this work was evaluated based on optical, electrical and structuralmore » characterization. Infrared microscopy was used to examine the internal crystalline structure of the samples. Most of the crystals grown during this work exhibited photorefractivity and photoconductivity. The resistivity of the vanadium doped crystals under dark conditions was found to be between 10 {sup 8} to 10 {sup 10} ohms cm. The resistivity decreased significantly in the presence of illumination indicating that the crystals were highly photoconductive. The photorefractive properties of the crystals grown during this project were characterized by two beam coupling. All of the measurements revealed a strong photorefractive nonlinear effect.« less

Crystal structure and physical properties of new Ca{sub 2}TGe{sub 3} (T = Pd and Pt) germanides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klimczuk, T., E-mail: tomasz.klimczuk@pg.gda.pl; Xie, Weiwei; Winiarski, M.J.

The crystallographic, electronic transport and thermal properties of Ca{sub 2}PdGe{sub 3} and Ca{sub 2}PtGe{sub 3} are reported. The compounds crystalize in an ordered variant of the AlB{sub 2} crystal structure, in space group P6/mmm, with the lattice parameters a = 8.4876(4) Å/8.4503(5) Å and c = 4.1911(3) Å/4.2302(3) Å for Ca{sub 2}PdGe{sub 3} and Ca{sub 2}PtGe{sub 3}, respectively. The resistivity data exhibit metallic behavior with residual-resistivity-ratios (RRR) of 13 for Ca{sub 2}PdGe{sub 3} and 6.5 for Ca{sub 2}PtGe{sub 3}. No superconducting transition is observed down to 0.4 K. Specific heat studies reveal similar values of the Debye temperatures and Sommerfeldmore » coefficients: Θ{sub D} = 298 K, γ = 4.1 mJ mol{sup −1} K{sup −2} and Θ{sub D} = 305 K, γ = 3.2 mJ mol{sup −1} K{sup −2} for Ca{sub 2}PdGe{sub 3} and Ca{sub 2}PtGe{sub 3}, respectively. The low value of γ is in agreement with the electronic structure calculations.« less

The bifoil photodyne: a photonic crystal oscillator.

PubMed

Lugo, J E; Doti, R; Sanchez, N; de la Mora, M B; del Rio, J A; Faubert, J

2014-01-15

Optical tweezers is an example how to use light to generate a physical force. They have been used to levitate viruses, bacteria, cells, and sub cellular organisms. Nonetheless it would be beneficial to use such force to develop a new kind of applications. However the radiation pressure usually is small to think in moving larger objects. Currently, there is some research investigating novel photonic working principles to generate a higher force. Here, we studied theoretically and experimentally the induction of electromagnetic forces in one-dimensional photonic crystals when light impinges on the off-axis direction. The photonic structure consists of a micro-cavity like structure formed of two one-dimensional photonic crystals made of free-standing porous silicon, separated by a variable air gap and the working wavelength is 633 nm. We show experimental evidence of this force when the photonic structure is capable of making auto-oscillations and forced-oscillations. We measured peak displacements and velocities ranging from 2 up to 35 microns and 0.4 up to 2.1 mm/s with a power of 13 mW. Recent evidence showed that giant resonant light forces could induce average velocity values of 0.45 mm/s in microspheres embedded in water with 43 mW light power.

The bifoil photodyne: a photonic crystal oscillator

PubMed Central

Lugo, J. E.; Doti, R.; Sanchez, N.; de la Mora, M. B.; del Rio, J. A.; Faubert, J.

2014-01-01

Optical tweezers is an example how to use light to generate a physical force. They have been used to levitate viruses, bacteria, cells, and sub cellular organisms. Nonetheless it would be beneficial to use such force to develop a new kind of applications. However the radiation pressure usually is small to think in moving larger objects. Currently, there is some research investigating novel photonic working principles to generate a higher force. Here, we studied theoretically and experimentally the induction of electromagnetic forces in one-dimensional photonic crystals when light impinges on the off-axis direction. The photonic structure consists of a micro-cavity like structure formed of two one-dimensional photonic crystals made of free-standing porous silicon, separated by a variable air gap and the working wavelength is 633 nm. We show experimental evidence of this force when the photonic structure is capable of making auto-oscillations and forced-oscillations. We measured peak displacements and velocities ranging from 2 up to 35 microns and 0.4 up to 2.1 mm/s with a power of 13 mW. Recent evidence showed that giant resonant light forces could induce average velocity values of 0.45 mm/s in microspheres embedded in water with 43 mW light power. PMID:24423985

Structural evolution of gypsum under high pressure: single-crystal X-ray experiments revisited

NASA Astrophysics Data System (ADS)

Li, Tsung-Lung; Lee, Pei-Lun

2018-05-01

The structures of gypsum at pressures up to approximately 4 GPa are studied with density functional theory (DFT) and thoroughly compared with single-crystal X-ray diffraction experiments reported in the literature [Comodi et al. in (Am Miner 93:1530-1537, 2008)]. It is found that the exchange-correlation density functional revPBE (revised Perdew-Burke-Ernzerhof) in conjunction with a nonlocal van der Waals (vdW) correction is capable of modeling the lattice constants, axial compressibility, and bulk modulus with good accuracy, suggesting that the inclusion of the vdW functional is crucially important for understanding the structure of hydrous minerals. To gain further physical insights, the geometric parameters associated with the constituting components of gypsum (water molecules, SO4 tetrahedra, and CaO8 polyhedra) are analyzed and compared with the experimental values. DFT simulations show that, under pressure, the polyhedral layers remain as nearly planar sheets of interconnecting SO4 tetrahedra and CaO8 polyhedra without further crinkling. DFT analysis on the layer compressibility along the major crystal axis reveals that, in contrast to experimental reports, the hydrous interlayer is less compressible than the polyhedral layer. Squeezed by the lateral pressure, the water molecules in the hydrous interlayer become better affixed along the major axis, making the interlayer harder to compress along this axis.

Initial Steps of Rubicene Film Growth on Silicon Dioxide.

PubMed

Scherwitzl, Boris; Lukesch, Walter; Hirzer, Andreas; Albering, Jörg; Leising, Günther; Resel, Roland; Winkler, Adolf

2013-02-28

The film growth of the conjugated organic molecule rubicene on silicon dioxide was studied in detail. Since no structural data of the condensed material were available, we first produced high quality single crystals from solution and determined the crystal structure. This high purity material was used to prepare ultrathin films under ultrahigh vacuum conditions, by physical vapor deposition. Thermal desorption spectroscopy (TDS) was applied to delineate the adsorption and desorption kinetics. It could be shown that the initial sticking coefficient is only 0.2 ± 0.05, but the sticking coefficient increases with increasing coverage. TDS further revealed that first a closed, weakly bound bilayer develops (wetting layer), which dewets after further deposition of rubicene, leading to an island-like layer. These islands are crystalline and exhibit the same structure as the solution grown crystals. The orientation of the crystallites is with the (001) plane parallel to the substrate. A dewetting of the closed bilayer was also observed when the film was exposed to air. Furthermore, Ostwald ripening of the island-like film takes place under ambient conditions, leading to films composed of few, large crystallites. From TDS, we determined the heat of evaporation from the multilayer islands to be 1.47 eV, whereas the desorption energy from the first layer is only 1.25 eV.

Initial Steps of Rubicene Film Growth on Silicon Dioxide

PubMed Central

2013-01-01

The film growth of the conjugated organic molecule rubicene on silicon dioxide was studied in detail. Since no structural data of the condensed material were available, we first produced high quality single crystals from solution and determined the crystal structure. This high purity material was used to prepare ultrathin films under ultrahigh vacuum conditions, by physical vapor deposition. Thermal desorption spectroscopy (TDS) was applied to delineate the adsorption and desorption kinetics. It could be shown that the initial sticking coefficient is only 0.2 ± 0.05, but the sticking coefficient increases with increasing coverage. TDS further revealed that first a closed, weakly bound bilayer develops (wetting layer), which dewets after further deposition of rubicene, leading to an island-like layer. These islands are crystalline and exhibit the same structure as the solution grown crystals. The orientation of the crystallites is with the (001) plane parallel to the substrate. A dewetting of the closed bilayer was also observed when the film was exposed to air. Furthermore, Ostwald ripening of the island-like film takes place under ambient conditions, leading to films composed of few, large crystallites. From TDS, we determined the heat of evaporation from the multilayer islands to be 1.47 eV, whereas the desorption energy from the first layer is only 1.25 eV. PMID:23476720

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Hao; Materials Science Program, University of Wisconsin, Madison, Wisconsin 53706; Stewart, Derek A., E-mail: derek.stewart@hgst.com

Metal oxide resistive memory devices based on Ta{sub 2}O{sub 5} have demonstrated high switching speed, long endurance, and low set voltage. However, the physical origin of this improved performance is still unclear. Ta{sub 2}O{sub 5} is an important archetype of a class of materials that possess an adaptive crystal structure that can respond easily to the presence of defects. Using first principles nudged elastic band calculations, we show that this adaptive crystal structure leads to low energy barriers for in-plane diffusion of oxygen vacancies in λ phase Ta{sub 2}O{sub 5}. Identified diffusion paths are associated with collective motion of neighboringmore » atoms. The overall vacancy diffusion is anisotropic with higher diffusion barriers found for oxygen vacancy movement between Ta-O planes. Coupled with the fact that oxygen vacancy formation energy in Ta{sub 2}O{sub 5} is relatively small, our calculated low diffusion barriers can help explain the low set voltage in Ta{sub 2}O{sub 5} based resistive memory devices. Our work shows that other oxides with adaptive crystal structures could serve as potential candidates for resistive random access memory devices. We also discuss some general characteristics for ideal resistive RAM oxides that could be used in future computational material searches.« less

Crystal growth and characterization of bulk Sb2Te3 topological insulator

NASA Astrophysics Data System (ADS)

Sultana, Rabia; Gurjar, Ganesh; Patnaik, S.; Awana, V. P. S.

2018-04-01

The Sb2Te3 crystals are grown using the conventional self flux method via solid state reaction route, by melting constituent elements (Sb and Te) at high temperature (850 °C), followed by slow cooling (2 °C/h). As grown Sb2Te3 crystals are analysed for various physical properties by x-ray diffraction (XRD), Raman Spectroscopy, Scanning Electron Microscopy (SEM) coupled with Energy Dispersive x-ray Spectroscopy (EDAX) and electrical measurements under magnetic field (6 Tesla) down to low temperature (2.5 K). The XRD pattern revealed the growth of synthesized Sb2Te3 sample along (00l) plane, whereas the SEM along with EDAX measurements displayed the layered structure with near stoichiometric composition, without foreign contamination. The Raman scattering studies displayed known ({{{{A}}}1{{g}}}1, {{{{E}}}{{g}}}2 and {{{{A}}}1{{g}}}2) vibrational modes for the studied Sb2Te3. The temperature dependent electrical resistivity measurements illustrated the metallic nature of the as grown Sb2Te3 single crystal. Further, the magneto—transport studies represented linear positive magneto-resistance (MR) reaching up to 80% at 2.5 K under an applied field of 6 Tesla. The weak anti localization (WAL) related low field (±2 Tesla) magneto-conductance at low temperatures (2.5 K and 20 K) has been analysed and discussed using the Hikami—Larkin—Nagaoka (HLN) model. Summarily, the short letter reports an easy and versatile method for crystal growth of bulk Sb2Te3 topological insulator (TI) and its brief physical property characterization.

High-throughput determination of structural phase diagram and constituent phases using GRENDEL

NASA Astrophysics Data System (ADS)

Kusne, A. G.; Keller, D.; Anderson, A.; Zaban, A.; Takeuchi, I.

2015-11-01

Advances in high-throughput materials fabrication and characterization techniques have resulted in faster rates of data collection and rapidly growing volumes of experimental data. To convert this mass of information into actionable knowledge of material process-structure-property relationships requires high-throughput data analysis techniques. This work explores the use of the Graph-based endmember extraction and labeling (GRENDEL) algorithm as a high-throughput method for analyzing structural data from combinatorial libraries, specifically, to determine phase diagrams and constituent phases from both x-ray diffraction and Raman spectral data. The GRENDEL algorithm utilizes a set of physical constraints to optimize results and provides a framework by which additional physics-based constraints can be easily incorporated. GRENDEL also permits the integration of database data as shown by the use of critically evaluated data from the Inorganic Crystal Structure Database in the x-ray diffraction data analysis. Also the Sunburst radial tree map is demonstrated as a tool to visualize material structure-property relationships found through graph based analysis.

Asymptotics for metamaterials and photonic crystals

PubMed Central

Antonakakis, T.; Craster, R. V.; Guenneau, S.

2013-01-01

Metamaterial and photonic crystal structures are central to modern optics and are typically created from multiple elementary repeating cells. We demonstrate how one replaces such structures asymptotically by a continuum, and therefore by a set of equations, that captures the behaviour of potentially high-frequency waves propagating through a periodic medium. The high-frequency homogenization that we use recovers the classical homogenization coefficients in the low-frequency long-wavelength limit. The theory is specifically developed in electromagnetics for two-dimensional square lattices where every cell contains an arbitrary hole with Neumann boundary conditions at its surface and implemented numerically for cylinders and split-ring resonators. Illustrative numerical examples include lensing via all-angle negative refraction, as well as omni-directive antenna, endoscope and cloaking effects. We also highlight the importance of choosing the correct Brillouin zone and the potential of missing interesting physical effects depending upon the path chosen. PMID:23633908

Electric-field-stimulated protein mechanics

PubMed Central

Hekstra, Doeke R.; White, K. Ian; Socolich, Michael A.; Henning, Robert W.; Šrajer, Vukica; Ranganathan, Rama

2017-01-01

The internal mechanics of proteins—the coordinated motions of amino acids and the pattern of forces constraining these motions—connects protein structure to function. Here we describe a new method combining the application of strong electric field pulses to protein crystals with time-resolved X-ray crystallography to observe conformational changes in spatial and temporal detail. Using a human PDZ domain (LNX2PDZ2) as a model system, we show that protein crystals tolerate electric field pulses strong enough to drive concerted motions on the sub-microsecond timescale. The induced motions are subtle, involve diverse physical mechanisms, and occur throughout the protein structure. The global pattern of electric-field-induced motions is consistent with both local and allosteric conformational changes naturally induced by ligand binding, including at conserved functional sites in the PDZ domain family. This work lays the foundation for comprehensive experimental study of the mechanical basis of protein function. PMID:27926732

Broad bandwidth and 600 μm length photonic crystal fiber polarization filter at the communication window of 1.55 μm

NASA Astrophysics Data System (ADS)

Zhang, Zhen; Li, Shuguang; Liu, Qiang; Zhang, Shuhuan; Wang, Yujun; Wu, Junjun

2018-02-01

A broad bandwidth and 600-μm length photonic crystal fiber polarization filter at the communication window of 1.55 μm is proposed. The physical parameters are analyzed by the finite element method. In the structure, the loss is 705.81 dB/cm for y-polarized mode and 24.06 dB/cm for x-polarized mode at the wavelength of 1.55 μm; the y-polarized mode will be filtered out because of this property. The bandwidth of an extinction ratio (ER) better than -20 dB is 65 nm when the filter length is 600 μm, and the ER is -41 dB at the communication wavelength of 1.55 μm. The filter structure is simple and easy to produce, and it can be used to produce a single-polarization filter.

Revisiting the blind tests in crystal structure prediction: accurate energy ranking of molecular crystals.

PubMed

Asmadi, Aldi; Neumann, Marcus A; Kendrick, John; Girard, Pascale; Perrin, Marc-Antoine; Leusen, Frank J J

2009-12-24

In the 2007 blind test of crystal structure prediction hosted by the Cambridge Crystallographic Data Centre (CCDC), a hybrid DFT/MM method correctly ranked each of the four experimental structures as having the lowest lattice energy of all the crystal structures predicted for each molecule. The work presented here further validates this hybrid method by optimizing the crystal structures (experimental and submitted) of the first three CCDC blind tests held in 1999, 2001, and 2004. Except for the crystal structures of compound IX, all structures were reminimized and ranked according to their lattice energies. The hybrid method computes the lattice energy of a crystal structure as the sum of the DFT total energy and a van der Waals (dispersion) energy correction. Considering all four blind tests, the crystal structure with the lowest lattice energy corresponds to the experimentally observed structure for 12 out of 14 molecules. Moreover, good geometrical agreement is observed between the structures determined by the hybrid method and those measured experimentally. In comparison with the correct submissions made by the blind test participants, all hybrid optimized crystal structures (apart from compound II) have the smallest calculated root mean squared deviations from the experimentally observed structures. It is predicted that a new polymorph of compound V exists under pressure.

Three reversible polymorphic copper(I) complexes triggered by ligand conformation: insights into polymorphic crystal habit and luminescent properties.

PubMed

Chai, Wenxiang; Hong, Mingwei; Song, Li; Jia, Guohua; Shi, Hongsheng; Guo, Jiayu; Shu, Kangying; Guo, Bing; Zhang, Yicheng; You, Wenwu; Chen, Xueyuan

2015-05-04

Three luminescent polymorphs based on a new copper(I) complex Cu(2-QBO)(PPh3)PF6 (1, PPh3 = triphenylphosphine, 2-QBO = 2-(2'-quinolyl)benzoxazole) have been synthesized and characterized by FT-IR, UV-vis, elemental analyses, and single-crystal X-ray diffraction analyses. Each polymorph can reversibly convert from one to another through appropriate procedures. Interestingly, such interconversion can be distinguished by their intrinsic crystal morphologies and colors (namely α, dark yellow plate, β, orange block, γ, light yellow needle) as well as photoluminescent (PL) properties. X-ray crystal structure analyses of these three polymorphs show three different supramolecular structures from 1D to 3D, which are expected to be responsible for the formation of three different crystal morphologies such as needle, plate, and block. Combination of the experimental data with DFT calculations on these three polymorphs reveals that the polymorphic interconversion is triggered by the conformation isomerization of the 2-QBO ligand and can be successfully controlled by the polarity of the process solvents (affecting the molecular dipole moment) and thermodynamics (affecting the molecular total energy). It is also found that the different crystal colors of polymorphs and their PL properties are derived from different θ values (dihedral angle between benzoxazolyl and quinolyl group of the 2-QBO ligand) and P-Cu-P angles based on TD-DFT calculations. Moreover, an interesting phase interconversion between γ and β has also been found under different temperature, and this result is consistent with the DFT calculations in which the total energy of β is larger than that of γ. This polymorphism provides a good model to study the relationship between the structure and the physical properties in luminescent copper(I) complexes as well as some profound insights into their PL properties.

Identifying barriers to charge-carriers in the bulk and surface regions of Cu2ZnSnS4 nanocrystal films by x-ray absorption fine structures (XAFSs)

NASA Astrophysics Data System (ADS)

Turnbull, Matthew J.; Vaccarello, Daniel; Yiu, Yun Mui; Sham, Tsun-Kong; Ding, Zhifeng

2016-11-01

Solar cell performance is most affected by the quality of the light absorber layer. For thin-film devices, this becomes a two-fold problem of maintaining a low-cost design with well-ordered nanocrystal (NC) structure. The use of Cu2ZnSnS4 (CZTS) NCs as the light absorber films forms an ideal low-cost design, but the quaternary structure makes it difficult to maintain a well-ordered layer without the use of high-temperature treatments. There is little understanding of how CZTS NC structures affect the photoconversion efficiency, the charge-carriers, and therefore the performance of the device manufactured from it. To examine these relationships, the measured photoresponse from the photo-generation of charge-carrier electron-hole pairs was compared against the crystal structure, as short-range and long-range crystal orders for the films. The photoresponse simplifies the electronic properties into three basic steps that can be associated with changes in energy levels within the band structure. These changes result in the formation of barriers to charge-carrier flow. The extent of these barriers was determined using synchrotron-based X-ray absorbance fine structure to probe the individual metal centers in the film, and comparing these to molecular simulations of the ideal extended x-ray absorbance fine structure scattering. This allowed for the quantification of bond lengths, and thus an interpretation of the distortions in the crystal lattice. The various characteristics of the photoresponse were then correlated to the crystallographic order and used to gain physical insight into barriers to charge-carriers in the bulk and surface regions of CZTS films.

The Physics and Chemistry of Materials

NASA Astrophysics Data System (ADS)

Gersten, Joel I.; Smith, Frederick W.

2001-06-01

A comprehensive introduction to the structure, properties, and applications of materials This title provides the first unified treatment for the broad subject of materials. Authors Gersten and Smith use a fundamental approach to define the structure and properties of a wide range of solids on the basis of the local chemical bonding and atomic order present in the material. Emphasizing the physical and chemical origins of material properties, the book focuses on the most technologically important materials being utilized and developed by scientists and engineers. Appropriate for use in advanced materials courses, The Physics and Chemistry of Materials provides the background information necessary to assimilate the current academic and patent literature on materials and their applications. Problem sets, illustrations, and helpful tables complete this well-rounded new treatment. Five sections cover these important topics: * Structure of materials, including crystal structure, bonding in solids, diffraction and the reciprocal lattice, and order and disorder in solids * Physical properties of materials, including electrical, thermal, optical, magnetic, and mechanical properties * Classes of materials, including semiconductors, superconductors, magnetic materials, and optical materials in addition to metals, ceramics, polymers, dielectrics, and ferroelectrics * A section on surfaces, thin films, interfaces, and multilayers discusses the effects of spatial discontinuities in the physical and chemical structure of materials * A section on synthesis and processing examines the effects of synthesis on the structure and properties of various materials This book is enhanced by a Web-based supplement that offers advanced material together with an entire electronic chapter on the characterization of materials. The Physics and Chemistry of Materials is a complete introduction to the structure and properties of materials for students and an excellent reference for scientists and engineers.

Measurement of physical characteristics of materials by ultrasonic methods

DOEpatents

Lu, Wei-yang; Min, Shermann

1998-01-01

A method is described for determining and evaluating physical characteristics of a material. In particular, the present invention provides for determining and evaluating the anisotropic characteristics of materials, especially those resulting from such manufacturing processes as rolling, forming, extruding, drawing, forging, etc. In operation, a complex ultrasonic wave is created in the material of interest by any method. The wave form may be any combination of wave types and modes and is not limited to fundamental plate modes. The velocity of propagation of selected components which make up the complex ultrasonic wave are measured and evaluated to determine the physical characteristics of the material including, texture, strain/stress, grain size, crystal structure, etc.

Measurement of physical characteristics of materials by ultrasonic methods

DOEpatents

Lu, W.Y.; Min, S.

1998-09-08

A method is described for determining and evaluating physical characteristics of a material. In particular, the present invention provides for determining and evaluating the anisotropic characteristics of materials, especially those resulting from such manufacturing processes as rolling, forming, extruding, drawing, forging, etc. In operation, a complex ultrasonic wave is created in the material of interest by any method. The wave form may be any combination of wave types and modes and is not limited to fundamental plate modes. The velocity of propagation of selected components which make up the complex ultrasonic wave are measured and evaluated to determine the physical characteristics of the material including, texture, strain/stress, grain size, crystal structure, etc. 14 figs.

Proton transfer and hydrogen bonding in the organic solid state: a combined XRD/XPS/ssNMR study of 17 organic acid-base complexes.

PubMed

Stevens, Joanna S; Byard, Stephen J; Seaton, Colin C; Sadiq, Ghazala; Davey, Roger J; Schroeder, Sven L M

2014-01-21

The properties of nitrogen centres acting either as hydrogen-bond or Brønsted acceptors in solid molecular acid-base complexes have been probed by N 1s X-ray photoelectron spectroscopy (XPS) as well as (15)N solid-state nuclear magnetic resonance (ssNMR) spectroscopy and are interpreted with reference to local crystallographic structure information provided by X-ray diffraction (XRD). We have previously shown that the strong chemical shift of the N 1s binding energy associated with the protonation of nitrogen centres unequivocally distinguishes protonated (salt) from hydrogen-bonded (co-crystal) nitrogen species. This result is further supported by significant ssNMR shifts to low frequency, which occur with proton transfer from the acid to the base component. Generally, only minor chemical shifts occur upon co-crystal formation, unless a strong hydrogen bond is formed. CASTEP density functional theory (DFT) calculations of (15)N ssNMR isotropic chemical shifts correlate well with the experimental data, confirming that computational predictions of H-bond strengths and associated ssNMR chemical shifts allow the identification of salt and co-crystal structures (NMR crystallography). The excellent agreement between the conclusions drawn by XPS and the combined CASTEP/ssNMR investigations opens up a reliable avenue for local structure characterization in molecular systems even in the absence of crystal structure information, for example for non-crystalline or amorphous matter. The range of 17 different systems investigated in this study demonstrates the generic nature of this approach, which will be applicable to many other molecular materials in organic, physical, and materials chemistry.

Phase stability, crystal structure and magnetism in (U1-xNbx)2 Ni21B6 and (UyNb1-y)3Ni20B6

NASA Astrophysics Data System (ADS)

Provino, Alessia; Bhattacharya, Amitava; Dhar, Sudesh K.; Pani, Marcella; Gatti, Flavio; Paudyal, Durga; Manfrinetti, Pietro

Ternary phases with composition T2M21X6 and T3M20X6 (T = transition metal; M = 3 d metal; X = B, C, P) are reported to crystallize with the W2Cr21C6-type and Mg3Ni20B6-type, respectively (ternary ordered derivatives of the cubic Cr23C6-type, cF116). They attract interest due to their refractory, mechanical, and peculiar magnetic properties. Literature data on these compounds only concern apparently stoichiometric 2:21:6 and 3:20:6 phases. Often only nominal composition has been reported, with few structural refinements and no measurements of physical properties. Lack of detailed stoichiometry and crystallographic data does not allow sufficient understanding of the crystal chemistry and properties of these compounds. We studied stability, crystal structure and magnetism of (U1-xNbx)2 Ni21B6 and (UyNb1-y)3Ni20B6; stable phases are U2Ni21B6 and Nb3Ni20B6, as also confirmed by theoretical calculations. The two pristine compounds solubilize Nb and U, respectively, up to a given extent. The substitution of U by Nb leads to a structural change from the W2Cr21C6- to the Mg3Ni20B6-type. While U2Ni21B6 is a Pauli paramagnet (itinerant non-magnetic state of U-5 f electrons), in agreement with literature, magnetization data for (UyNb1-y)3 Ni20B6 show itinerant ferromagnetism with TC >300 K.

Integrating Condensed Matter Physics into a Liberal Arts Physics Curriculum

NASA Astrophysics Data System (ADS)

Collett, Jeffrey

2008-03-01

The emergence of nanoscale science into the popular consciousness presents an opportunity to attract and retain future condensed matter scientists. We inject nanoscale physics into recruiting activities and into the introductory and the core portions of the curriculum. Laboratory involvement and research opportunity play important roles in maintaining student engagement. We use inexpensive scanning tunneling (STM) and atomic force (AFM) microscopes to introduce students to nanoscale structure early in their college careers. Although the physics of tip-surface interactions is sophisticated, the resulting images can be interpreted intuitively. We use the STM in introductory modern physics to explore quantum tunneling and the properties of electrons at surfaces. An interdisciplinary course in nanoscience and nanotechnology course team-taught with chemists looks at nanoscale phenomena in physics, chemistry, and biology. Core quantum and statistical physics courses look at effects of quantum mechanics and quantum statistics in degenerate systems. An upper level solid-state physics course takes up traditional condensed matter topics from a structural perspective by beginning with a study of both elastic and inelastic scattering of x-rays from crystalline solids and liquid crystals. Students encounter reciprocal space concepts through the analysis of laboratory scattering data and by the development of the scattering theory. The course then examines the importance of scattering processes in band structure and in electrical and thermal conduction. A segment of the course is devoted to surface physics and nanostructures where we explore the effects of restricting particles to two-dimensional surfaces, one-dimensional wires, and zero-dimensional quantum dots.

The nature of the mineral component of bone and the mechanism of calcification.

PubMed

Glimcher, M J

1987-01-01

From the physical chemical standpoint, the formation of a solid phase of Ca-P in bone represents a phase transformation, a process exemplified by the formation of ice from water. Considering the structural complexity and abundance of highly organized macromolecules in the cells and extracellular tissue spaces of mineralized tissues generally and in bone particularly, it is inconceivable that this phase transformation occurs by homogeneous nucleation, i.e., without the active participation of an organic component acting as a nucleator. This is almost surely true in biologic mineralization in general. Electron micrographs and low-angle neutron and X-ray diffraction studies clearly show that calcification of collagen fibrils occurs in an extremely intimate and highly organized fashion: initiation of crystal formation within the collagen fibrils in the hole zone region, with the long axes (c-axis) of the crystals aligned roughly parallel to the long axis of the fibril within which they are located. Crystals are initially formed in hole zone regions within individual fibrils separated by unmineralized regions. Calcification is initiated in spatially distinct nucleation sites. This indicates that such regions within a single, undirectional fibril represents independent sites for heterogeneous nucleation. Clearly, sites where mineralization is initiated in adjacent collagen fibrils are even further separated, emphasizing even more clearly that the process of progressive calcification of the collagen fibrils and therefore of the tissue is characterized principally by the presence of increasing numbers of independent nucleation sites within additional hole zone regions of the collagen fibrils. The increase in the mass of Ca-P apatite accrues principally by multiplication of more crystals, mostly by secondary nucleation from the crystals initially deposited in the hole zone region. Very little additional growth of the crystals occurs with time, the additional increase in mineral mass being principally the result of increase in the number of crystals (multiplication), not size of the crystals (crystal growth). The crystals within the collagen fibers grow in number and possibly in size to extend into the overlap zone of the collagen fibrils ("pores") so that all of the available space within the fibrils, which has possibly expanded in volume from its uncalcified level, is eventually occupied by the mineral crystals. It must be recognized that the calcification of separate tissue components and compartments (collagen, mitochondria, matrix vesicles) must be an independent physical chemical event.(ABSTRACT TRUNCATED AT 400 WORDS)

Neutron scattering as a probe of liquid crystal polymer-reinforced composite materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hjelm, R.P.; Douglas, E.P.; Benicewicz, B.C.

1995-12-31

This is the final report of a three-year Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This research project sought to obtain nanoscale and molecular level information on the mechanism of reinforcement in liquid crystal polymer (LCP)-reinforced composites, to realize molecular-reinforced LCP composites, and to test the validity of the concept of molecular reinforcement. Small-angle neutron scattering was used to study the structures in the ternary phase diagram of LCP with liquid crystal thermosets and solvent on length scales ranging from 1-100 nm. The goal of the scattering measurements is to understand the phase morphologymore » and degree of segregation of the reinforcing and matrix components. This information helps elucidate the physics of self assembly in these systems. This work provides an experimental basis for a microengineering approach to composites of vastly improved properties.« less

Toda hierarchies and their applications

NASA Astrophysics Data System (ADS)

Takasaki, Kanehisa

2018-05-01

The 2D Toda hierarchy occupies a central position in the family of integrable hierarchies of the Toda type. The 1D Toda hierarchy and the Ablowitz–Ladik (aka relativistic Toda) hierarchy can be derived from the 2D Toda hierarchy as reductions. These integrable hierarchies have been applied to various problems of mathematics and mathematical physics since 1990s. A recent example is a series of studies on models of statistical mechanics called the melting crystal model. This research has revealed that the aforementioned two reductions of the 2D Toda hierarchy underlie two different melting crystal models. Technical clues are a fermionic realization of the quantum torus algebra, special algebraic relations therein called shift symmetries, and a matrix factorization problem. The two melting crystal models thus exhibit remarkable similarity with the Hermitian and unitary matrix models for which the two reductions of the 2D Toda hierarchy play the role of fundamental integrable structures.

Triboluminescence from Pharmaceutical Formulations.

PubMed

Smith, Casey J; Griffin, Scott R; Eakins, Gregory S; Deng, Fengyuan; White, Julia K; Thirunahari, Satyanarayana; Ramakrishnan, Srividya; Sangupta, Atanu; Zhang, Siwei; Novak, Julie; Liu, Zhen; Rhodes, Timothy; Simpson, Garth J

2018-06-05

Triboluminescence (TL) is shown to enable selective detection of trace crystallinity within nominally amorphous solid dispersions (ASDs). ASDs are increasingly used for the preparation of pharmaceutical formulations, the physical stability of which can be negatively impacted by trace crystallinity introduced during manufacturing or storage. In the present study, TL measurements of a model ASD consisting of griseofulvin in polyethylene glycol produced limits of detection of 140 ppm. Separate studies of the particle size dependence of sucrose crystals and the dependence on polymorphism in clopidogrel bisulfate particles are both consistent with a mechanism for TL closely linked to the piezoelectric response of the crystalline fraction. Whereas disordered polymeric materials cannot support piezoelectric activity, molecular crystals produced from homochiral molecules adopt crystal structures that are overwhelmingly symmetry-allowed for piezoelectricity. Consequently, TL may provide a broadly applicable and simple experimental route for sensitive detection of trace crystallinity within nominally amorphous materials.

Ferromagnetic Switching of Knotted Vector Fields in Liquid Crystal Colloids.

PubMed

Zhang, Qiaoxuan; Ackerman, Paul J; Liu, Qingkun; Smalyukh, Ivan I

2015-08-28

We experimentally realize polydomain and monodomain chiral ferromagnetic liquid crystal colloids that exhibit solitonic and knotted vector field configurations. Formed by dispersions of ferromagnetic nanoplatelets in chiral nematic liquid crystals, these colloidal ferromagnets exhibit spontaneous long-range alignment of magnetic dipole moments of individual platelets, giving rise to a continuum of the magnetization field M(r). Competing effects of surface confinement and chirality prompt spontaneous formation and enable the optical generation of localized twisted solitonic structures with double-twist tubes and torus knots of M(r), which exhibit a strong sensitivity to the direction of weak magnetic fields ∼1  mT. Numerical modeling, implemented through free energy minimization to arrive at a field-dependent three-dimensional M(r), shows a good agreement with experiments and provides insights into the torus knot topology of observed field configurations and the corresponding physical underpinnings.

Crystallization of amorphous silicon thin films deposited by PECVD on nickel-metalized porous silicon.

PubMed

Ben Slama, Sonia; Hajji, Messaoud; Ezzaouia, Hatem

2012-08-17

Porous silicon layers were elaborated by electrochemical etching of heavily doped p-type silicon substrates. Metallization of porous silicon was carried out by immersion of substrates in diluted aqueous solution of nickel. Amorphous silicon thin films were deposited by plasma-enhanced chemical vapor deposition on metalized porous layers. Deposited amorphous thin films were crystallized under vacuum at 750°C. Obtained results from structural, optical, and electrical characterizations show that thermal annealing of amorphous silicon deposited on Ni-metalized porous silicon leads to an enhancement in the crystalline quality and physical properties of the silicon thin films. The improvement in the quality of the film is due to the crystallization of the amorphous film during annealing. This simple and easy method can be used to produce silicon thin films with high quality suitable for thin film solar cell applications.

Crystallization of amorphous silicon thin films deposited by PECVD on nickel-metalized porous silicon

PubMed Central

2012-01-01

Porous silicon layers were elaborated by electrochemical etching of heavily doped p-type silicon substrates. Metallization of porous silicon was carried out by immersion of substrates in diluted aqueous solution of nickel. Amorphous silicon thin films were deposited by plasma-enhanced chemical vapor deposition on metalized porous layers. Deposited amorphous thin films were crystallized under vacuum at 750°C. Obtained results from structural, optical, and electrical characterizations show that thermal annealing of amorphous silicon deposited on Ni-metalized porous silicon leads to an enhancement in the crystalline quality and physical properties of the silicon thin films. The improvement in the quality of the film is due to the crystallization of the amorphous film during annealing. This simple and easy method can be used to produce silicon thin films with high quality suitable for thin film solar cell applications. PMID:22901341

Solution to the Phase Problem Using Multibeam X-Ray Diffraction.

NASA Astrophysics Data System (ADS)

Shen, Qun

Multi-beam x-ray diffraction, especially the asymmetry effect in the virtual Bragg scattering case, has been proved to provide useful phase information on the structure factors that are involved in the scattering process. A perturbation theory has been developed to provide an analytical expression for the diffracted wave field in virtual Bragg scattering situations, which explains the physical origin of the asymmetry effect. Two experiments on the (202) reflection of benzil, using 3.5 keV x-rays, have shown that the asymmetry effect is visible in a mosaic non-centrosymmetric organic crystal. The results do not depend on the shape of the crystal, hence proving that the method is universally applicable. A practical method to obtain arbitrary values of the phase triplet, based on the perturbation theory, has been developed and shown to work in the case of non-centrosymmetric crystals like benzil.

Growth of single-crystalline cobalt silicide nanowires and their field emission property

PubMed Central

2013-01-01

In this work, cobalt silicide nanowires were synthesized by chemical vapor deposition processes on Si (100) substrates with anhydrous cobalt chloride (CoCl2) as precursors. Processing parameters, including the temperature of Si (100) substrates, the gas flow rate, and the pressure of reactions were varied and studied; additionally, the physical properties of the cobalt silicide nanowires were measured. It was found that single-crystal CoSi nanowires were grown at 850°C ~ 880°C and at a lower gas flow rate, while single-crystal Co2Si nanowires were grown at 880°C ~ 900°C. The crystal structure and growth direction were identified, and the growth mechanism was proposed as well. This study with field emission measurements demonstrates that CoSi nanowires are attractive choices for future applications in field emitters. PMID:23819795

Application of Bottlebrush Block Copolymers as Photonic Crystals.

PubMed

Liberman-Martin, Allegra L; Chu, Crystal K; Grubbs, Robert H

2017-07-01

Brush block copolymers are a class of comb polymers that feature polymeric side chains densely grafted to a linear backbone. These polymers display interesting properties due to their dense functionality, low entanglement, and ability to rapidly self-assemble to highly ordered nanostructures. The ability to prepare brush polymers with precise structures has been enabled by advancements in controlled polymerization techniques. This Feature Article highlights the development of brush block copolymers as photonic crystals that can reflect visible to near-infrared wavelengths of light. Fabrication of these materials relies on polymer self-assembly processes to achieve nanoscale ordering, which allows for the rapid preparation of photonic crystals from common organic chemical feedstocks. The characteristic physical properties of brush block copolymers are discussed, along with methods for their preparation. Strategies to induce self-assembly at ambient temperatures and the use of blending techniques to tune photonic properties are emphasized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalysts for electrochemical generation of oxygen

NASA Technical Reports Server (NTRS)

Hagans, P.; Yeager, E.

1978-01-01

Single crystal surfaces of platinum and gold and transition metal oxides of the spinel type were studied to find more effective catalysts for the electrolytic evolution of oxygen and to understand the mechanism and kinetics for the electrocatalysis in relation to the surface electronic and lattice properties of the catalyst. The single crystal studies involve the use of low energy electron diffraction (LEED) and Auger electron spectroscopy as complementary tools to the electrochemical measurements. Modifications to the transfer system and to the thin-layer electrochemical cell used to facilitate the transfer between the ultrahigh vacuum environment of the electron surface physics equipment and the electrochemical environment with a minimal possibility of changes in the surface structure, are described. The electrosorption underpotential deposition of Pb onto the Au(111), (100) and (110) single crystal surfaces with the thin-layer cell-LEED-Auger system is discussed as well as the synthesis of spinels for oxygen evolution studies.

Single crystal neutron diffraction of hydrous wadsleyite and the reason of sensitivity difference for hydration between upper and lower mantle transition zones

NASA Astrophysics Data System (ADS)

Purevjav, N.; Okuchi, T.; Tomioka, N.; Wang, X.; Hoffmann, C.

2016-12-01

Evidences from seismological and mineralogical studies increasingly indicates that water has been transported from the oceans into the Earth's deep mantle, where the mantle transition zone is believed to be the largest reservoir of this transported water. Wadsleyite and ringwoodite are the major constituents and the most important host minerals absorbing this type of water in the transition zone. These minerals are capable of storing the entire mass of the oceans as a hidden reservoirs. In order to understand the effects of such water on the physical properties and chemical evolution of the Earth's interior, it is essential to determine where in the crystal structure the hydration occurs, and which chemical bonds are altered and weakened after hydration. Here we show the result of a neutron single-crystal Laue diffraction study of hydrous wadsleyite. A crystal of homogenously-hydrated wadsleyite involving 1.4 wt. % of H2O was synthesized by our recently-established slow cooling method, which was an effective way to grow high quality large single crystals [1]. By analyzing this crystal using pulsed neutron beam, we demonstrated that the hydrogen atoms exchange only with Mg2+ at the one of the specific octahedron sites (M3) in wadsleyite. We also determined hydrogen's bonding distances and bonding angle. The results unambiguously demonstrated the unique mechanism of hydrogen incorporation into the wadsleyite crystal structure. We previously found that the hydrogen atoms exchanged with both Mg2+ and Si4+ sites simultaneously in the crystal structure of hydrous ringwoodite [2]. Therefore, the current results show that hydration mechanisms are qualitatively different between the upper and the lower transition zones in the wet mantle. The difference is a vital clue towards understanding why these mantle transition zone minerals show different sensitivity for water in their softening behaviors. In addition, we demonstrated that maximum water concentration in wadsleyite is strictly constrained by its full capacity into M3 site. Also, by this study we demonstrated that single-crystal neutron diffraction is a useful tool for quantitative analysis of H2O concentrations in nominally anhydrous minerals. [1] Okuchi et al., Amer. Miner., 2015; [2] Purevjav et al., Geophys. Res. Lett., 2014.

In vitro uses of biological cryoprotectants.

PubMed Central

Lillford, Peter J; Holt, Chris B

2002-01-01

Ice can be anything from a highly destructive agent in agriculture to a useful building material. Established industries are based on the known rules of physics and chemistry which allow some control of amounts of ice or ice crystal geometry. However, organisms have much more subtle requirements to maintain their delicate internal structure if they are to survive freezing. As a result they have selected specific molecules for freezing-point depression, osmotic regulation, ice nucleation and crystal growth inhibition. All these active species may have potential commercial use once they are identified, understood and produced at economic scales. We examine the progress made so far in extending biological subtlety into commercial processes, and look for prospects for further innovation. PMID:12171658

Large Scale Laser Crystallization of Solution-based Alumina-doped Zinc Oxide (AZO) Nanoinks for Highly Transparent Conductive Electrode

PubMed Central

Nian, Qiong; Callahan, Michael; Saei, Mojib; Look, David; Efstathiadis, Harry; Bailey, John; Cheng, Gary J.

2015-01-01

A new method combining aqueous solution printing with UV Laser crystallization (UVLC) and post annealing is developed to deposit highly transparent and conductive Aluminum doped Zinc Oxide (AZO) films. This technique is able to rapidly produce large area AZO films with better structural and optoelectronic properties than most high vacuum deposition, suggesting a potential large-scale manufacturing technique. The optoelectronic performance improvement attributes to UVLC and forming gas annealing (FMG) induced grain boundary density decrease and electron traps passivation at grain boundaries. The physical model and computational simulation developed in this work could be applied to thermal treatment of many other metal oxide films. PMID:26515670

Defect interactions in anisotropic two-dimensional fluids

NASA Astrophysics Data System (ADS)

Stannarius, Ralf; Harth, Kirsten

Disclinations in liquid crystals bear striking analogies to defect structures in a wide variety of physical systems, they are excellent models to study fundamental properties of defect interactions. Freely suspended smectic C films behave like quasi 2D polar nematics. An experimental procedure is introduced to capture high-strength disclinations in localized spots. After they are released in a controlled way, the motion of the mutually repelling topological charges is studied. We demonstrate that the classical models, based on elastic one-constant approximation, fail to describe their dynamics correctly. In realistic liquid crystals, the models work only in ideal configurations. In general, additional director walls modify interactions substantially. Funded by DFG within project STA 425/28-1.

ab initio MD simulations of geomaterials with ~1000 atoms

NASA Astrophysics Data System (ADS)

Martin, G. B.; Kirtman, B.; Spera, F. J.

2009-12-01

In the last two decades, ab initio studies of materials using Density Functional Theory (DFT) have increased exponentially in popularity. DFT codes are now used routinely to simulate properties of geomaterials--mainly silicates and geochemically important metals such as Fe. These materials are ubiquitous in the Earth’s mantle and core and in terrestrial exoplanets. Because of computational limitations, most First Principles Molecular Dynamics (FPMD) calculations are done on systems of only ~100 atoms for a few picoseconds. While this approach can be useful for calculating physical quantities related to crystal structure, vibrational frequency, and other lattice-scale properties (especially in crystals), it is statistically marginal for duplicating physical properties of the liquid state like transport and structure. In MD simulations in the NEV ensemble, temperature (T), and pressure (P) fluctuations scale as N-1/2; small particle number (N) systems are therefore characterized by greater statistical state point location uncertainty than large N systems. Previous studies have used codes such as VASP where CPU time increases with N2, making calculations with N much greater than 100 impractical. SIESTA (Soler, et al. 2002) is a DFT code that enables electronic structure and MD computations on larger systems (N~103) by making some approximations, such as localized numerical orbitals, that would be useful in modeling some properties of geomaterials. Here we test the applicability of SIESTA to simulate geosilicates, both hydrous and anhydrous, in the solid and liquid state. We have used SIESTA for lattice calculations of brucite, Mg(OH)2, that compare very well to experiment and calculations using CRYSTAL, another DFT code. Good agreement between more classical DFT calculations and SIESTA is needed to justify study of geosilicates using SIESTA across a range of pressures and temperatures relevant to the Earth’s interior. Thus, it is useful to adjust parameters in SIESTA in accordance with calculations from CRYSTAL as a check on feasibility. Results are reported here that suggest SIESTA may indeed be useful to model silicate liquids at very high T and P.

4D visualization of embryonic, structural crystallization by single-pulse microscopy

PubMed Central

Kwon, Oh-Hoon; Barwick, Brett; Park, Hyun Soon; Baskin, J. Spencer; Zewail, Ahmed H.

2008-01-01

In many physical and biological systems the transition from an amorphous to ordered native structure involves complex energy landscapes, and understanding such transformations requires not only their thermodynamics but also the structural dynamics during the process. Here, we extend our 4D visualization method with electron imaging to include the study of irreversible processes with a single pulse in the same ultrafast electron microscope (UEM) as used before in the single-electron mode for the study of reversible processes. With this augmentation, we report on the transformation of amorphous to crystalline structure with silicon as an example. A single heating pulse was used to initiate crystallization from the amorphous phase while a single packet of electrons imaged selectively in space the transformation as the structure continuously changes with time. From the evolution of crystallinity in real time and the changes in morphology, for nanosecond and femtosecond pulse heating, we describe two types of processes, one that occurs at early time and involves a nondiffusive motion and another that takes place on a longer time scale. Similar mechanisms of two distinct time scales may perhaps be important in biomolecular folding. PMID:18562291

Effects of the iodine incorporation on the structure and physical properties of Ge-Sb-Se chalcogenide glasses

NASA Astrophysics Data System (ADS)

Wang, Yaling; Xu, Junfeng; Cheng, Hu; Chang, Fang'e.; Jian, Zengyun

2018-01-01

(100-x)(Ge23Se67Sb10)-xI (x = 0, 3, 5, 7, 10 wt%) chalcohalide glasses were prepared by the traditional melt-quenched method. The structure and physical properties were analyzed by using XRD, TMA, FTIR and Vickers hardness tester. It was found that the glass structure trends to crystallization with increase of iodine content. The values of infrared transmittance decrease from 62% to 35% in the range of 2.5-16 μm with increasing iodine content. The density decreases from 4.62 ± 0.3 g cm-3 to 4.31 ± 0.3 g cm-3, the hardness decreases from 164.9 ± 0.5 kg mm-2 to 154.6 ± 0.5 kg mm-2. The glass transition point Tg decreases from 267 °C to 205 °C, while the thermal expansion coefficient increases with iodine content.

Ground Based Program for the Physical Analysis of Macromolecular Crystal Growth

NASA Technical Reports Server (NTRS)

Malkin, Alexander J.

1998-01-01

During the past year we have focused on application of in situ Atomic Force Microscopy (AFM) for studies of the growth mechanisms and kinetics of crystallization for different macromolecular systems. Mechanisms of macrostep formation and their decay, which are important in understanding of defect formation, were studied on the surfaces of thaumatin, catalase, canavalin and lysozyme crystals. Experiments revealed that step bunching on crystalline surfaces occurred either due to two- or three-dimensional nucleation on the terraces of vicinal slopes or as a result of uneven step generation by complex dislocation sources. No step bunching arising from interaction of individual steps in the course of the experiment was observed. The molecular structure of the growth steps for thaumatin and lipase crystals were deduced. It was further shown that growth step advance occurs by incorporation of single protein molecules. In singular directions growth steps move by one-dimensional nucleation on step edges followed by lateral growth. One-dimensional nuclei have different sizes, less then a single unit cell, varying for different directions of step movement. There is no roughness due to thermal fluctuations, and each protein molecule which incorporated into the step remained. Growth kinetics for catalase crystals was investigated over wide supersaturation ranges. Strong directional kinetic anisotropy in the tangential step growth rates in different directions was seen. The influence of impurities on growth kinetics and cessation of macromolecular crystals was studied. Thus, for catalase, in addition to pronounced impurity effects on the kinetics of crystallization, we were also able to directly observe adsorption of some impurities. At low supersaturation we repeatedly observed filaments which formed from impurity molecules sedimenting on the surfaces. Similar filaments were observed on the surfaces of thaumatin, canavalin and STMV crystals as well, but the frequency was low compared with catalase crystallization. Cessation of growth of xylanase and lysozyme crystals was also observed and appeared to be a consequence of the formation of dense impurity adsorption layers. Attachment: "An in situ AFM investigation of catalase crystallization", "Atomic force microscopy studies of living cells: visualization of motility, division, aggregation, transformation, and apoptosis", AFM studies on mechanisms of nucleation and growth of macromolecular crystals", and "In situ atomic force microscopy studies of surface morphology, growth kinetics, defect structure and dissolution in macromolecular crystallization".

First Principles Investigation of the Geometrical and Electrochemical Properties of Na4P

NASA Astrophysics Data System (ADS)

Rush, Larry E., Jr.; Holzwarth, N. A. W.

First principles simulations are used to examine the structural and physical properties of Na4P2S6 in comparison with its Li4P2S6 analog. Four model structures are considered including the C 2 / m structure recently reported by Kuhn and co-workers from their analysis of single crystals of Na4P2S6, and three structures related to the P63 / mcm structure with P site disorder found in 1982 by Mercier and co-workers from their analysis of single crystals of Li4P2S6. The computational results indicate that both Na4P2S6 and Li4P2S6 have the same disordered ground state structures consistent with the P63 / mcm space group, while the optimized C 2 / m structures have higher energies by 0.1 eV and 0.4 eV per formula unit for Na4P2S6 and Li4P2S6, respectively. Simulations of ion migration suggest that Na4P2S6 may have more favorable ionic conductivity compared to Li4P2S6. Supported by NSF Grant DMR-1105485 and DMR-1507942.

Crystal engineering of ibuprofen compounds: From molecule to crystal structure to morphology prediction by computational simulation and experimental study

NASA Astrophysics Data System (ADS)

Zhang, Min; Liang, Zuozhong; Wu, Fei; Chen, Jian-Feng; Xue, Chunyu; Zhao, Hong

2017-06-01

We selected the crystal structures of ibuprofen with seven common space groups (Cc, P21/c, P212121, P21, Pbca, Pna21, and Pbcn), which was generated from ibuprofen molecule by molecular simulation. The predicted crystal structures of ibuprofen with space group P21/c has the lowest total energy and the largest density, which is nearly indistinguishable with experimental result. In addition, the XRD patterns for predicted crystal structure are highly consistent with recrystallization from solvent of ibuprofen. That indicates that the simulation can accurately predict the crystal structure of ibuprofen from the molecule. Furthermore, based on this crystal structure, we predicted the crystal habit in vacuum using the attachment energy (AE) method and considered solvent effects in a systematic way using the modified attachment energy (MAE) model. The simulation can accurately construct a complete process from molecule to crystal structure to morphology prediction. Experimentally, we observed crystal morphologies in four different polarity solvents compounds (ethanol, acetonitrile, ethyl acetate, and toluene). We found that the aspect ratio decreases of crystal habits in this ibuprofen system were found to vary with increasing solvent relative polarity. Besides, the modified crystal morphologies are in good agreement with the observed experimental morphologies. Finally, this work may guide computer-aided design of the desirable crystal morphology.

Color changing photonic crystals detect blast exposure

PubMed Central

Cullen, D. Kacy; Xu, Yongan; Reneer, Dexter V.; Browne, Kevin D.; Geddes, James W.; Yang, Shu; Smith, Douglas H.

2010-01-01

Blast-induced traumatic brain injury (bTBI) is the “signature wound” of the current wars in Iraq and Afghanistan. However, with no objective information of relative blast exposure, warfighters with bTBI may not receive appropriate medical care and are at risk of being returned to the battlefield. Accordingly, we have created a colorimetric blast injury dosimeter (BID) that exploits material failure of photonic crystals to detect blast exposure. Appearing like a colored sticker, the BID is fabricated in photosensitive polymers via multi-beam interference lithography. Although very stable in the presence of heat, cold or physical impact, sculpted micro- and nano-structures of the BID are physically altered in a precise manner by blast exposure, resulting in color changes that correspond with blast intensity. This approach offers a lightweight, power-free sensor that can be readily interpreted by the naked eye. Importantly, with future refinement this technology may be deployed to identify soldiers exposed to blast at levels suggested to be supra-threshold for non-impact blast-induced mild TBI. PMID:21040795

Applications of the Cambridge Structural Database in organic chemistry and crystal chemistry.

PubMed

Allen, Frank H; Motherwell, W D Samuel

2002-06-01

The Cambridge Structural Database (CSD) and its associated software systems have formed the basis for more than 800 research applications in structural chemistry, crystallography and the life sciences. Relevant references, dating from the mid-1970s, and brief synopses of these papers are collected in a database, DBUse, which is freely available via the CCDC website. This database has been used to review research applications of the CSD in organic chemistry, including supramolecular applications, and in organic crystal chemistry. The review concentrates on applications that have been published since 1990 and covers a wide range of topics, including structure correlation, conformational analysis, hydrogen bonding and other intermolecular interactions, studies of crystal packing, extended structural motifs, crystal engineering and polymorphism, and crystal structure prediction. Applications of CSD information in studies of crystal structure precision, the determination of crystal structures from powder diffraction data, together with applications in chemical informatics, are also discussed.

Protein Crystals as Novel Catalytic Materials.

PubMed

Margolin, Alexey L.; Navia, Manuel A.

2001-06-18

In this era of molecular biology, protein crystallization is often considered to be a necessary first step in obtaining structural information through X-ray diffraction analysis. In a different light, protein crystals can also be thought of as materials, whose chemical and physical properties make them broadly attractive and useful across a larger spectrum of disciplines. The full potential of these protein crystalline materials has been severely restricted in practice, however, both by their inherent fragility, and by strongly held skepticism concerning their routine and predictable growth, formulation, and practical application. Fortunately, these problems have turned out to be solvable. A systematic exploration of the biophysics and biochemistry of protein crystallization has shown that one can dependably create new protein crystalline materials more or less at will. In turn, these crystals can be readily strengthened, both chemically and mechanically, to make them suitable for practical commercialization. Today, these novel materials are used as industrial catalysts on a commercial scale, in bioremediation and "green chemistry" applications, and in enantioselective chromatography of pharmaceuticals and fine chemicals. In the near future, their utility will expand, to include the purification of protein drugs, formulation of direct protein therapeutics, and development of adjuvant-less vaccines.

Perovskite Materials: Solar Cell and Optoelectronic Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Bin; Geohegan, David B; Xiao, Kai

2017-01-01

Hybrid organometallic trihalide perovskites are promising candidates in the applications for next-generation, high-performance, low-cost optoelectronic devices, including photovoltaics, light emitting diodes, and photodetectors. Particularly, the solar cells based on this type of materials have reached 22% lab scale power conversion efficiency in only about seven years, comparable to the other thin film photovoltaic technologies. Hybrid perovskite materials not only exhibit superior optoelectronic properties, but also show many interesting physical properties such as ion migration and defect physics, which may allow the exploration of more device functionalities. In this article, the fundamental understanding of the interrelationships between crystal structure, electronic structure,more » and material properties is discussed. Various chemical synthesis and processing methods for superior device performance in solar cells and optoelectronic devices are reviewed.« less

Optomechanics of two- and three-dimensional soft photonic crystals

NASA Astrophysics Data System (ADS)

Krishnan, Dwarak

Soft photonic crystals are a class of periodic dielectric structures that undergo highly nonlinear deformation due to strain or other external stimulus such as temperature, pH etc. This can in turn dramatically affect optical properties such as light transmittance. Moreover certain classes of lithographically fabricated structures undergo some structural distortion due to the effects of processing, eventually affecting the optical properties of the final photonic crystal. In this work, we study the deformation mechanics of soft photonic crystal structures using realistic physics-based models and leverage that understanding to explain the optomechanics of actual 2-D and 3-D soft photonic crystals undergoing similar symmetry breaking nonlinear deformations. We first study the optomechanics of two classes of 3-D soft photonic crystals: (1) hydrogel and (2) elastomer based material systems. The hydrogel based inverse face-centered-cubic structure undergoes swelling with change in pH of the surrounding fluid. The inverse structure is a network of bulky domains with thin ligament-like connections, and it undergoes a pattern transformation from FCC to L11 as a result of swelling. A continuum scale poroelasticity based coupled fluid-diffusion FEM model is developed to accurately predict this mechanical behavior. Light transmittance simulation results qualitatively explain the experimentally observed trends in the optical behavior with pH change. The elastomer based, lithographically fabricated material experiences shrinkage induced distortion upon processing. This behavior is modeled using FEM with the material represented by a neo-Hookean constitutive law. The light transmittance calculations for normal incidence are carried out using the transfer matrix method and a good comparison is obtained for the positions of first and second order reflectance peaks. A unit cell based approach is taken to compute the photonic bandstructure to estimate light propagation through the structure for other angles of light incidence. To obtain a detailed picture of the change in optical properties due to a pattern transformation, we study simple 2-D elastomer photonic crystals which undergo an interesting structural pattern transformation from simple circular holes to alternately oriented ellipses in a square lattice due to uniaxial compression. The incident light does not have any effect on the properties of the elastomer material. A decomposition of the deformation gradient quickly shows that the pattern transformation is induced by alternating rotations of the interstitial regions and the bending of interconnecting ligaments. Numerical simulations of light transmittance using vector element based FEM analysis of Maxwells equations shows changes in the light energy localization within the material especially in the high energy/low wavelength regions of the spectra. Additionally, with bandstructure calculations on a unit cell of the structure, the optomechanical behavior is completely explained. Finally, computational evidence is provided for a hypothetical 2-D photonic crystal made of a light-sensitive material, which undergoes a structural pattern transformation primarily due to the effect of incident light. The model takes into account the order kinetics of optically induced isomerization (of trans to cis configuration) in the azobenzene-liquid crystal elastomer to compute the transformational strain. This strain, in turn, deforms the structure and hence changes its periodicity and dielectric properties and thus affects the manner in which light gets localized within the material system. This consequently changes the profile of the imposed transformational strain on the deformed structure. The macroscopic strain history shows that prior to the mechanical instability that causes the pattern transformation, there is a period of structural relaxation which initiates the pattern transformation. After the symmetry breaking pattern transformation, the photonic bandstructure is altered significantly. Light does not get localized in the spot regions anymore and stress relaxation dominates. Due to this, the compressive macroscopic strain of the pattern transformed structure starts to decrease indicating a possible cyclical behavior.

Validation of experimental molecular crystal structures with dispersion-corrected density functional theory calculations.

PubMed

van de Streek, Jacco; Neumann, Marcus A

2010-10-01

This paper describes the validation of a dispersion-corrected density functional theory (d-DFT) method for the purpose of assessing the correctness of experimental organic crystal structures and enhancing the information content of purely experimental data. 241 experimental organic crystal structures from the August 2008 issue of Acta Cryst. Section E were energy-minimized in full, including unit-cell parameters. The differences between the experimental and the minimized crystal structures were subjected to statistical analysis. The r.m.s. Cartesian displacement excluding H atoms upon energy minimization with flexible unit-cell parameters is selected as a pertinent indicator of the correctness of a crystal structure. All 241 experimental crystal structures are reproduced very well: the average r.m.s. Cartesian displacement for the 241 crystal structures, including 16 disordered structures, is only 0.095 Å (0.084 Å for the 225 ordered structures). R.m.s. Cartesian displacements above 0.25 A either indicate incorrect experimental crystal structures or reveal interesting structural features such as exceptionally large temperature effects, incorrectly modelled disorder or symmetry breaking H atoms. After validation, the method is applied to nine examples that are known to be ambiguous or subtly incorrect.

A Novel Energetic Perchlorate Amine Salt: Synthesis, Properties, and Density Functional Theory Calculation

NASA Astrophysics Data System (ADS)

Ma, Peng; Pan, Yong; Jiang, Juncheng; Zhu, Shunguan

2017-10-01

A novel explosive, ethylenediamine triethylenediamine tetraperchlorate (ETT), was synthesized by a rapid " one-pot" method. The molecular and crystal structures of ETT were determined by X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) spectroscopy. The purity of the ETT was characterized by hydrogen nuclear magnetic resonance (H-NMR) spectra and elemental analysis (EA). The chemical and physical properties of the co-crystal ETT were further explored including impact sensitivity, velocity of detonation, and thermal behavior. The impact sensitivity of the ETT (h50% = 9.50 cm) is much lower than that of its components, ethylenediamine diperchlorate (ED) (h50% = 5.60 cm) and triethylenediamine diperchlorate (TD) (h50% = 2.10 cm). The measured detonation velocity is 8956 m/s (ρ = 1.873 g/cm3), which is much higher than that of TNT (6900 m/s) or RDX (8350 m/s). The co-crystal ETT shows a unique thermal behavior with a decomposition peak temperature at 365 °C. Band structure and density of states (DOS) of the ETT were confirmed by the CASTEP code. The first-principles tight-binding method within the general gradient approximation (GGA) was employed to study the electronic band structure as well as the DOS and Fermi energy. Hirshfeld surfaces were applied to analyze the intermolecular interactions in the co-crystal, and the results showed that weak interaction was dominantly mediated by H … O hydrogen bond. By analyzing the bond length at different temperatures, N-H covalent bond is the trigger bond for the ETT.

Hyper-branched CdTe nanostructures based on the self-assembling of quantum dots and their optical properties.

PubMed

Pan, Ling-Yun; Pan, Gen-Cai; Zhang, Yong-Lai; Gao, Bing-Rong; Dai, Zhen-Wen

2013-02-01

As the priority of interconnects and active components in nanoscale optical and electronic devices, three-dimensional hyper-branched nanostructures came into focus of research. Recently, a novel crystallization route, named as "nonclassical crystallization," has been reported for three-dimensional nanostructuring. In this process, Quantum dots are used as building blocks for the construction of the whole hyper-branched structures instead of ions or single-molecules in conventional crystallization. The specialty of these nanostructures is the inheritability of pristine quantum dots' physical integrity because of their polycrystalline structures, such as quantum confinement effect and thus the luminescence. Moreover, since a longer diffusion length could exist in polycrystalline nanostructures due to the dramatically decreased distance between pristine quantum dots, the exciton-exciton interaction would be different with well dispersed quantum dots and single crystal nanostructures. This may be a benefit for electron transport in solar cell application. Therefore, it is very necessary to investigate the exciton-exciton interaction in such kind of polycrystalline nanostructures and their optical properites for solar cell application. In this research, we report a novel CdTe hyper-branched nanostructures based on self-assembly of CdTe quantum dots. Each branch shows polycrystalline with pristine quantum dots as the building units. Both steady state and time-resolved spectroscopy were performed to investigate the properties of carrier transport. Steady state optical properties of pristine quantum dots are well inherited by formed structures. While a suppressed multi-exciton recombination rate was observed. This result supports the percolation of carriers through the branches' network.

Growth kinetics of physical vapor transport processes: Crystal growth of the optoelectronic material mercurous chloride

NASA Technical Reports Server (NTRS)

Singh, N. B.; Duval, W. M.

1991-01-01

Physical vapor transport processes were studied for the purpose of identifying the magnitude of convective effects on the crystal growth process. The effects of convection on crystal quality were were studied by varying the aspect ratio and those thermal conditions which ultimately affect thermal convection during physical vapor transport. An important outcome of the present study was the observation that the convection growth rate increased up to a certain value and then dropped to a constant value for high aspect ratios. This indicated that a very complex transport had occurred which could not be explained by linear stability theory. Better quality crystals grown at a low Rayleigh number confirmed that improved properties are possible in convectionless environments.

New multicell model for describing the atomic structure of La{sub 3}Ga{sub 5}SiO{sub 14} piezoelectric crystal: Unit cells of different compositions in the same single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dudka, A. P., E-mail: dudka@ns.crys.ras.ru

2017-03-15

Accurate X-ray diffraction study of langasite (La{sub 3}Ga{sub 5}SiO{sub 14}) single crystal has been performed using the data obtained on a diffractometer equipped with a CCD area detector at 295 and 90.5 K. Within the known La{sub 3}Ga{sub 5}SiO{sub 14} model, Ga and Si cations jointly occupy the 2d site. A new model of a “multicell” consisting of two different unit cells is proposed. Gallium atoms occupy the 2d site in one of these cells, and silicon atoms occupy this site in the other cell; all other atoms correspondingly coordinate these cations. This structure implements various physical properties exhibited bymore » langasite family crystals. The conclusions are based on processing four data sets obtained with a high resolution (sin θ/λ ≤ 1.35 Å{sup –1}), the results reproduced in repeated experiments, and the high relative precision of the study (sp. gr. P321, Z = 1; at 295 K, a = 8.1652(6) Å, c = 5.0958(5) Å, R/wR = 0.68/0.68%, 3927 independent reflections; at 90.5 K, a = 8.1559(4) Å, c = 5.0913(6) Å, R/wR = 0.92/0.93%, 3928 reflections).« less

In-situ and real-time growth observation of high-quality protein crystals under quasi-microgravity on earth.

PubMed

Nakamura, Akira; Ohtsuka, Jun; Kashiwagi, Tatsuki; Numoto, Nobutaka; Hirota, Noriyuki; Ode, Takahiro; Okada, Hidehiko; Nagata, Koji; Kiyohara, Motosuke; Suzuki, Ei-Ichiro; Kita, Akiko; Wada, Hitoshi; Tanokura, Masaru

2016-02-26

Precise protein structure determination provides significant information on life science research, although high-quality crystals are not easily obtained. We developed a system for producing high-quality protein crystals with high throughput. Using this system, gravity-controlled crystallization are made possible by a magnetic microgravity environment. In addition, in-situ and real-time observation and time-lapse imaging of crystal growth are feasible for over 200 solution samples independently. In this paper, we also report results of crystallization experiments for two protein samples. Crystals grown in the system exhibited magnetic orientation and showed higher and more homogeneous quality compared with the control crystals. The structural analysis reveals that making use of the magnetic microgravity during the crystallization process helps us to build a well-refined protein structure model, which has no significant structural differences with a control structure. Therefore, the system contributes to improvement in efficiency of structural analysis for "difficult" proteins, such as membrane proteins and supermolecular complexes.

Ice crystallization in ultrafine water-salt aerosols: nucleation, ice-solution equilibrium, and internal structure.

PubMed

Hudait, Arpa; Molinero, Valeria

2014-06-04

Atmospheric aerosols have a strong influence on Earth's climate. Elucidating the physical state and internal structure of atmospheric aqueous aerosols is essential to predict their gas and water uptake, and the locus and rate of atmospherically important heterogeneous reactions. Ultrafine aerosols with sizes between 3 and 15 nm have been detected in large numbers in the troposphere and tropopause. Nanoscopic aerosols arising from bubble bursting of natural and artificial seawater have been identified in laboratory and field experiments. The internal structure and phase state of these aerosols, however, cannot yet be determined in experiments. Here we use molecular simulations to investigate the phase behavior and internal structure of liquid, vitrified, and crystallized water-salt ultrafine aerosols with radii from 2.5 to 9.5 nm and with up to 10% moles of ions. We find that both ice crystallization and vitrification of the nanodroplets lead to demixing of pure water from the solutions. Vitrification of aqueous nanodroplets yields nanodomains of pure low-density amorphous ice in coexistence with vitrified solute rich aqueous glass. The melting temperature of ice in the aerosols decreases monotonically with an increase of solute fraction and decrease of radius. The simulations reveal that nucleation of ice occurs homogeneously at the subsurface of the water-salt nanoparticles. Subsequent ice growth yields phase-segregated, internally mixed, aerosols with two phases in equilibrium: a concentrated water-salt amorphous mixture and a spherical cap-like ice nanophase. The surface of the crystallized aerosols is heterogeneous, with ice and solution exposed to the vapor. Free energy calculations indicate that as the concentration of salt in the particles, the advance of the crystallization, or the size of the particles increase, the stability of the spherical cap structure increases with respect to the alternative structure in which a core of ice is fully surrounded by solution. We predict that micrometer-sized particles and nanoparticles have the same equilibrium internal structure. The variation of liquid-vapor surface tension with solute concentration is a key factor in determining whether a solution-embedded ice core or vapor-exposed ice cap is the equilibrium structure of the aerosols. In agreement with experiments, we predict that the structure of mixed-phase HNO3-water particles, representative of polar stratospheric clouds, consists of an ice core surrounded by freeze-concentrated solution. The results of this work are important to determine the phase state and internal structure of sea spray ultrafine aerosols and other mixed-phase particles under atmospherically relevant conditions.

Nanoscale Strontium Titanate Sheets and Crystals

NASA Astrophysics Data System (ADS)

Tilka, Jack Andrew

The physical properties of materials are dominated by their structure and composition. Insight into the structure of complex oxide materials has the potential to improve our understanding and eventually control of their physical properties. This PhD thesis reports the development of characterization and fabrication techniques relevant to improving the scientific understanding of complex oxide materials. The work presented here has two components. I report a way to use ideas that were originally developed in semiconductor processing to control the elastic strain state and crystallization process of the model complex oxide SrTiO3. An additional component is an important series of advances in the analysis of diffraction patterns acquired with focused x-ray nanobeams. The fabrication and characterization of nanoscale SrTiO3 has been experimentally shown to allow the introduction of elastic strain into SrTiO3. The creation of thin SrTiO3 crystals from (001)-oriented SrTiO3 bulk single crystals using focused ion beam milling techniques yields sheets with submicron thickness and arbitrary orientation within the (001) plane. Synchrotron x-ray nanodiffraction experiments show that the SrTiO 3 sheets have rocking curves with angular widths less than 0.02°. These widths are less than a factor of two larger than bulk SrTiO3, which shows that the sheets are suitable substrates for epitaxial thin film growth. A precisely selected elastic strain can be introduced into the SrTiO 3 sheets using a silicon nitride stressor layer. Synchrotron x-ray nanodiffraction studies show that the strain introduced in the SrTiO3 sheets is on the order of 10-4, matching the predictions of an elastic model. This approach to elastic strain sharing in complex oxides allows the strain to be selected within a wide and continuous range of values, an effect not achievable in heteroepitaxy on rigid substrates. An additional fabrication technique is also evaluated here based on the crystallization of SrTiO3 from initially amorphous thin films. This process is known as solid-phase epitaxy in two-dimensional samples but is just beginning to be explored in more complex geometries. I report experiments in both homoepitaxy and heteroepitaxy including measurements of crystal growth rates and the crystallographic orientations of crystals formed in this way. The lateral growth rates are consistent with previously measured vertical growth. This result indicated that previous work on vertical solid-phase epitaxy could be extended into lateral solid-phase epitaxy, which has the power to be applied to complicated non-planar geometries. The highly coherent and tightly focused x-ray beams produced by hard x-ray light sources enable the nanoscale structural characterization of materials but are accompanied by significant challenges in the interpretation of diffraction and scattering patterns. I report here a series of methods that expand the range of physical problems that can be accurately captured by coherent x-ray optical simulations. My approach has been to expand simulations methods to include arbitrary x-ray incident angles and arbitrary epitaxial heterostructures. I first applied these methods to extract the misorientation of lattice planes and the strain of individual layers of Si/SiGe heterostructures relevant to applications in quantum electronics. Further applications reported in this thesis are in probing defects created in the processing of SrTiO3 and in measuring the change in lattice parameter introduced into strained SrTiO3 sheets. The systematic interpretation of nanobeam diffraction patterns aids in the fabrication of SrTiO3 nanostructures.

Monte Carlo Study of Magnetic Properties of Mixed Spins in a Fullerene X 30 Y 30-Like Structure

NASA Astrophysics Data System (ADS)

Mhirech, A.; Aouini, S.; Alaoui-Ismaili, A.; Bahmad, L.

2018-03-01

In this work, inspiring form of the fullerene-C60 structures, we study the mixed X_{30} Y_{30} fullerene-like structure and investigate its magnetic properties. In a such a structure, the carbons are assumed to be replaced by magnetic atoms having spin moments σ = 1/2 and S = 1. Firstly, we elaborate the ground-state phase diagrams in different physical parameter planes. In a second stage, we investigate the exchange coupling interaction effects in the absence or presence of both external magnetic and crystal fields. Using the Monte Carlo method, we carried out a study of the system magnetic properties and the thermal behavior of such a system for the ferromagnetic case. It is found that the critical temperature increases when increasing the coupling exchange interactions. On the other hand, the coercive magnetic field increases also when increasing the coupling exchange interactions. However, this physical parameter decreases when increasing the reduced temperature.

Ground-based research of crystal growth of II-VI compound semiconductors by physical vapor transport

NASA Technical Reports Server (NTRS)

Volz, M. P.; Gillies, D. C.; Szofran, F. R.; Lehoczky, S. L.; Su, Ching-Hua; Sha, Yi-Gao; Zhou, W.; Dudley, M.; Liu, Hao-Chieh; Brebrick, R. F.;

Artificially structured thin-film materials and interfaces.

PubMed

Narayanamurti, V

1987-02-27

The ability to artificially structure new materials on an atomic scale by using advanced crystal growth methods such as molecular beam epitaxy and metal-organic chemical vapor deposition has recently led to the observation of unexpected new physical phenomena and to the creation of entirely new classes of devices. In particular, the growth of materials of variable band gap in technologically important semiconductors such as GaAs, InP, and silicon will be reviewed. Recent results of studies of multilayered structures and interfaces based on the use of advanced characterization techniques such as high-resolution transmission electron microscopy and scanning tunneling microscopy will be presented.

Protein Crystals Grow Purer in Space: Physics of Phenomena

NASA Technical Reports Server (NTRS)

Chernov, Alex A.

2000-01-01

This presentation will summarize the quantitative experimental and theoretical results obtained by B.R. Thomas, P.G. Vekilov, D.C. Carter, A.M. Holmes, W.K. Widierow and the Author, the team with expertise in physics, biochemistry, crystallography and engineering. Impurities inhomogeneously trapped by a growing crystal - e.g., producing sectorial structure and/or striations - may induce macroscopic internal stress in it if an impurity molecule has slightly (less than 10%) different shape or volume than the regular one(s) they replace. We tested for the first time plasticity and measured Young modulus E of the triclinic, not cross-linked lysozyme by triple point bending technique. Triclinic lysozyme crystals are purely elastic with E similar or equal to 1/5 (raised dot) 10 (exp 9) partial derivative yn/sq cm. The strength limit, sigma (sub c) similar or equal to 10 (exp -3)E similar or equal to Epsilon (sub c), where sigma (sub c) and epsilon (sub c) are critical stress and strain, respectively. Scaling E and sigma (sub c) with the lattice spacing suggests similar binding stiffness in inorganic and biomolecular crystals. The inhomogeneous internal stress may be resolved in these brittle crystals either by cracking or by creation of misoriented mosaic blocks during, not after growth. If each impurity molecule induces in the lattice elementary strain epsilon (sub 0) similar or equal to 3 (raised dot) 10 (exp -2) (this is maximal elementary strain that can arise at the supersaturation DELTA mu/kT similar or equal to 2 and macroscopic molecular concentration difference between subsequent macrolayers or growth sectors is partial derivativeC similar or equal to 5 (raised dot) 10 (exp -3), the internal strain epsilon similar or equal to epsilon (sub 0) partial derivative C similar or equal to 10 (exp -4). Mosaic misorientation resolving such strain is approximately 30 arcsec. Tenfold increase of impurity concentration may cause cracking. Estimates of stress in an isometric sectorial crystal show that lysozyme crystals can tolerate the stress till the size of 0.5mm. Dissolving mosaic lysozyme crystal shows that the mosaicity, indeed, is absent below that size.

Random close packing in protein cores

NASA Astrophysics Data System (ADS)

Ohern, Corey

Shortly after the determination of the first protein x-ray crystal structures, researchers analyzed their cores and reported packing fractions ϕ ~ 0 . 75 , a value that is similar to close packing equal-sized spheres. A limitation of these analyses was the use of `extended atom' models, rather than the more physically accurate `explicit hydrogen' model. The validity of using the explicit hydrogen model is proved by its ability to predict the side chain dihedral angle distributions observed in proteins. We employ the explicit hydrogen model to calculate the packing fraction of the cores of over 200 high resolution protein structures. We find that these protein cores have ϕ ~ 0 . 55 , which is comparable to random close-packing of non-spherical particles. This result provides a deeper understanding of the physical basis of protein structure that will enable predictions of the effects of amino acid mutations and design of new functional proteins. We gratefully acknowledge the support of the Raymond and Beverly Sackler Institute for Biological, Physical, and Engineering Sciences, National Library of Medicine training grant T15LM00705628 (J.C.G.), and National Science Foundation DMR-1307712 (L.R.).

High-speed prediction of crystal structures for organic molecules

NASA Astrophysics Data System (ADS)

Obata, Shigeaki; Goto, Hitoshi

2015-02-01

We developed a master-worker type parallel algorithm for allocating tasks of crystal structure optimizations to distributed compute nodes, in order to improve a performance of simulations for crystal structure predictions. The performance experiments were demonstrated on TUT-ADSIM supercomputer system (HITACHI HA8000-tc/HT210). The experimental results show that our parallel algorithm could achieve speed-ups of 214 and 179 times using 256 processor cores on crystal structure optimizations in predictions of crystal structures for 3-aza-bicyclo(3.3.1)nonane-2,4-dione and 2-diazo-3,5-cyclohexadiene-1-one, respectively. We expect that this parallel algorithm is always possible to reduce computational costs of any crystal structure predictions.

Phase Behavior and Physical Properties of New Biobased Ionic Liquid Crystals.

PubMed

Toledo Hijo, Ariel A C; Maximo, Guilherme J; Costa, Mariana C; Cunha, Rosiane L; Pereira, Jorge F B; Kurnia, Kiki A; Batista, Eduardo A C; Meirelles, Antonio J A

2017-04-13

Protic ionic liquids (PILs) have emerged as promising compounds and attracted the interest of the industry and the academy community, due to their easy preparation and unique properties. In the context of green chemistry, the use of biocompounds, such as fatty acids, for their synthesis could disclose a possible alternative way to produce ILs with a low or nontoxic effect and, consequently, expanding their applicability in biobased processes or in the development of bioproducts. This work addressed efforts to a better comprehension of the complex solid-[liquid crystal]-liquid thermodynamic equilibrium of 20 new PILs synthesized by using fatty acids commonly found in vegetable oils, as well as their rheological profile and self-assembling ability. The work revealed that their phase equilibrium and physical properties are significantly impacted by the structure of the ions used for their synthesis. The use of unsaturated fatty acids and bis(2-hydroxyethyl)ammonium for the synthesis of these biobased ILs led to a drastic decreasing of their melting temperatures. Also, the longest alkyl chain fatty acids promoted higher self-assembling and more stable mesophases. Besides their sustainable appeal, the marked high viscosity, non-Newtonian profile, and very low critical micellar concentration values of the PIL crystals here disclosed make them interesting renewable compounds with potential applications as emulsifiers, stabilizers, thickeners, or biolubricants.

Application of magnetoelastic materials in spatiotemporally modulated phononic crystals for nonreciprocal wave propagation

NASA Astrophysics Data System (ADS)

Ansari, M. H.; Attarzadeh, M. A.; Nouh, M.; Karami, M. Amin

2018-01-01

In this paper, a physical platform is proposed to change the properties of phononic crystals in space and time in order to achieve nonreciprocal wave transmission. The utilization of magnetoelastic materials in elastic phononic systems is studied. Material properties of magnetoelastic materials change significantly with an external magnetic field. This property is used to design systems with a desired wave propagation pattern. The properties of the magnetoelastic medium are changed in a traveling wave pattern, which changes in both space and time. A phononic crystal with such a modulation exhibits one-way wave propagation behavior. An extended transfer matrix method (TMM) is developed to model a system with time varying properties. The stop band and the pass band of a reciprocal and a nonreciprocal bar are found using this method. The TMM is used to find the transfer function of a magnetoelastic bar. The obtained results match those obtained via the theoretical Floquet-Bloch approach and numerical simulations. It is shown that the stop band in the transfer function of a system with temporal varying property for the forward wave propagation is different from the same in the backward wave propagation. The proposed configuration enables the physical realization of a class of smart structures that incorporates nonreciprocal wave propagation.

BH3-Amine and B(CH3)3-Amine Adducts as Additives for Liquid/Gel Hypergols and Solid Hybrid Rocket Motor Fuels: Property and Performance Predictions

DTIC Science & Technology

2013-12-01

and Thermolysis of Lithium, Magnesium Calcium and Strontium Tetraborate Complex Compounds With Triethylenediamine-Crystal Structure of 2BH3•C6H12N2...of Closed-Shell Atoms and Hydrides of the 1st-Row Elements. Journal of Chemical Physics 1988, 89 , 2193-2218. Petersson, G. A.; Tensfeldt, T

Enhanced renal image contrast by ethanol fixation in phase-contrast X-ray computed tomography.

PubMed

Shirai, Ryota; Kunii, Takuya; Yoneyama, Akio; Ooizumi, Takahito; Maruyama, Hiroko; Lwin, Thet Thet; Hyodo, Kazuyuki; Takeda, Tohoru

2014-07-01

Phase-contrast X-ray imaging using a crystal X-ray interferometer can depict the fine structures of biological objects without the use of a contrast agent. To obtain higher image contrast, fixation techniques have been examined with 100% ethanol and the commonly used 10% formalin, since ethanol causes increased density differences against background due to its physical properties and greater dehydration of soft tissue. Histological comparison was also performed. A phase-contrast X-ray system was used, fitted with a two-crystal X-ray interferometer at 35 keV X-ray energy. Fine structures, including cortex, tubules in the medulla, and the vessels of ethanol-fixed kidney could be visualized more clearly than that of formalin-fixed tissues. In the optical microscopic images, shrinkage of soft tissue and decreased luminal space were observed in ethanol-fixed kidney; and this change was significantly shown in the cortex and outer stripe of the outer medulla. The ethanol fixation technique enhances image contrast by approximately 2.7-3.2 times in the cortex and the outer stripe of the outer medulla; the effect of shrinkage and the physical effect of ethanol cause an increment of approximately 78% and 22%, respectively. Thus, the ethanol-fixation technique enables the image contrast to be enhanced in phase-contrast X-ray imaging.

Cation Exchange in Dynamic 3D Porous Magnets: Improvement of the Physical Properties.

PubMed

Grancha, Thais; Acosta, Alvaro; Cano, Joan; Ferrando-Soria, Jesús; Seoane, Beatriz; Gascon, Jorge; Pasán, Jorge; Armentano, Donatella; Pardo, Emilio

2015-11-16

We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li4{Mn4[Cu2(Me3mpba)2]3}·68H2O (2) and K4{Mn4[Cu2(Me3mpba)2]3}·69H2O (3) obtained-via alkali cation exchange in a single-crystal to single-crystal process-from the earlier reported anionic manganese(II)-copper(II) PCP of formula Na4{Mn4[Cu2(Me3mpba)2]3}·60H2O (1) [Me3mpba(4-) = N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1'-3') of 2.0 (1'), 12.0 (2'), and 20.0 K (3')]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures.

Influences of alkaline earth metal substitution on the crystal structure and physical properties of magnetic RuSr1.9A0.1GdCu2O8 (A = Ca, Sr, and Ba) superconductors.

PubMed

Hur, Su Gil; Park, Dae Hoon; Hwang, Seong-Ju; Kim, Seung Joo; Lee, J H; Lee, Sang Young

2005-11-24

We have investigated the effect of alkaline earth metal substitution on the crystal structure and physical properties of magnetic superconductors RuSr(1.9)A(0.1)GdCu(2)O(8) (A = Ca, Sr, and Ba) in order to probe an interaction between the magnetic coupling of the RuO(2) layer and the superconductivity of the CuO(2) layer. X-ray diffraction and X-ray absorption spectroscopic analyses demonstrate that the isovalent substitution of Sr ions with Ca or Ba ions makes it possible to tune the interlayer distance between the CuO(2) and the RuO(2) layers. From the measurements of electrical resistance and magnetic susceptibility, it was found that, in contrast to negligible change of magnetization, both of the alkaline earth metal substitutions lead to a notable depression of zero-resistance temperature T(c) (DeltaT(c) approximately 17-19 K). On the basis of the absence of a systematic correlation between the T(c) and the interlayer distance/magnetization, we have concluded that the internal magnetic field of the RuO(2) layer has insignificant influence on the superconducting property of the CuO(2) layer in the ruthenocuprate.

Isolation of a 250 million-year-old halotolerant bacterium from a primary salt crystal

NASA Astrophysics Data System (ADS)

Vreeland, Russell H.; Rosenzweig, William D.; Powers, Dennis W.

2000-10-01

Bacteria have been found associated with a variety of ancient samples, however few studies are generally accepted due to questions about sample quality and contamination. When Cano and Borucki isolated a strain of Bacillus sphaericus from an extinct bee trapped in 25-30 million-year-old amber, careful sample selection and stringent sterilization techniques were the keys to acceptance. Here we report the isolation and growth of a previously unrecognized spore-forming bacterium (Bacillus species, designated 2-9-3) from a brine inclusion within a 250million-year-old salt crystal from the Permian Salado Formation. Complete gene sequences of the 16S ribosomal DNA show that the organism is part of the lineage of Bacillus marismortui and Virgibacillus pantothenticus. Delicate crystal structures and sedimentary features indicate the salt has not recrystallized since formation. Samples were rejected if brine inclusions showed physical signs of possible contamination. Surfaces of salt crystal samples were sterilized with strong alkali and acid before extracting brines from inclusions. Sterilization procedures reduce the probability of contamination to less than 1 in 10 9.

Signature of dislocations and stacking faults of face-centred cubic nanocrystals in coherent X-ray diffraction patterns: a numerical study.

PubMed

Dupraz, Maxime; Beutier, Guillaume; Rodney, David; Mordehai, Dan; Verdier, Marc

2015-06-01

Crystal defects induce strong distortions in diffraction patterns. A single defect alone can yield strong and fine features that are observed in high-resolution diffraction experiments such as coherent X-ray diffraction. The case of face-centred cubic nanocrystals is studied numerically and the signatures of typical defects close to Bragg positions are identified. Crystals of a few tens of nanometres are modelled with realistic atomic potentials and 'relaxed' after introduction of well defined defects such as pure screw or edge dislocations, or Frank or prismatic loops. Diffraction patterns calculated in the kinematic approximation reveal various signatures of the defects depending on the Miller indices. They are strongly modified by the dissociation of the dislocations. Selection rules on the Miller indices are provided, to observe the maximum effect of given crystal defects in the initial and relaxed configurations. The effect of several physical and geometrical parameters such as stacking fault energy, crystal shape and defect position are discussed. The method is illustrated on a complex structure resulting from the simulated nanoindentation of a gold nanocrystal.

Signature of dislocations and stacking faults of face-centred cubic nanocrystals in coherent X-ray diffraction patterns: a numerical study1

PubMed Central

Dupraz, Maxime; Beutier, Guillaume; Rodney, David; Mordehai, Dan; Verdier, Marc

2015-01-01

Crystal defects induce strong distortions in diffraction patterns. A single defect alone can yield strong and fine features that are observed in high-resolution diffraction experiments such as coherent X-ray diffraction. The case of face-centred cubic nanocrystals is studied numerically and the signatures of typical defects close to Bragg positions are identified. Crystals of a few tens of nanometres are modelled with realistic atomic potentials and ‘relaxed’ after introduction of well defined defects such as pure screw or edge dislocations, or Frank or prismatic loops. Diffraction patterns calculated in the kinematic approximation reveal various signatures of the defects depending on the Miller indices. They are strongly modified by the dissociation of the dislocations. Selection rules on the Miller indices are provided, to observe the maximum effect of given crystal defects in the initial and relaxed configurations. The effect of several physical and geometrical parameters such as stacking fault energy, crystal shape and defect position are discussed. The method is illustrated on a complex structure resulting from the simulated nanoindentation of a gold nanocrystal. PMID:26089755

Isolation of a 250 million-year-old halotolerant bacterium from a primary salt crystal.

PubMed

Vreeland, R H; Rosenzweig, W D; Powers, D W

2000-10-19

Bacteria have been found associated with a variety of ancient samples, however few studies are generally accepted due to questions about sample quality and contamination. When Cano and Borucki isolated a strain of Bacillus sphaericus from an extinct bee trapped in 25-30 million-year-old amber, careful sample selection and stringent sterilization techniques were the keys to acceptance. Here we report the isolation and growth of a previously unrecognized spore-forming bacterium (Bacillus species, designated 2-9-3) from a brine inclusion within a 250 million-year-old salt crystal from the Permian Salado Formation. Complete gene sequences of the 16S ribosomal DNA show that the organism is part of the lineage of Bacillus marismortui and Virgibacillus pantothenticus. Delicate crystal structures and sedimentary features indicate the salt has not recrystallized since formation. Samples were rejected if brine inclusions showed physical signs of possible contamination. Surfaces of salt crystal samples were sterilized with strong alkali and acid before extracting brines from inclusions. Sterilization procedures reduce the probability of contamination to less than 1 in 10(9).

Amorphization and Directional Crystallization of Metals Confined in Carbon Nanotubes Investigated by in Situ Transmission Electron Microscopy.

PubMed

Tang, Dai-Ming; Ren, Cui-Lan; Lv, Ruitao; Yu, Wan-Jing; Hou, Peng-Xiang; Wang, Ming-Sheng; Wei, Xianlong; Xu, Zhi; Kawamoto, Naoyuki; Bando, Yoshio; Mitome, Masanori; Liu, Chang; Cheng, Hui-Ming; Golberg, Dmitri

2015-08-12

The hollow core of a carbon nanotube (CNT) provides a unique opportunity to explore the physics, chemistry, biology, and metallurgy of different materials confined in such nanospace. Here, we investigate the nonequilibrium metallurgical processes taking place inside CNTs by in situ transmission electron microscopy using CNTs as nanoscale resistively heated crucibles having encapsulated metal nanowires/crystals in their channels. Because of nanometer size of the system and intimate contact between the CNTs and confined metals, an efficient heat transfer and high cooling rates (∼10(13) K/s) were achieved as a result of a flash bias pulse followed by system natural quenching, leading to the formation of disordered amorphous-like structures in iron, cobalt, and gold. An intermediate state between crystalline and amorphous phases was discovered, revealing a memory effect of local short-to-medium range order during these phase transitions. Furthermore, subsequent directional crystallization of an amorphous iron nanowire formed by this method was realized under controlled Joule heating. High-density crystalline defects were generated during crystallization due to a confinement effect from the CNT and severe plastic deformation involved.

Postsynthetic Improvement of the Physical Properties in a Metal-Organic Framework through a Single Crystal to Single Crystal Transmetallation.

PubMed

Grancha, Thais; Ferrando-Soria, Jesús; Zhou, Hong-Cai; Gascon, Jorge; Seoane, Beatriz; Pasán, Jorge; Fabelo, Oscar; Julve, Miguel; Pardo, Emilio

2015-05-26

A single crystal to single crystal transmetallation process takes place in the three-dimensional (3D) metal-organic framework (MOF) of formula Mg(II) 2 {Mg(II) 4 [Cu(II) 2 (Me3 mpba)2 ]3 }⋅45 H2 O (1; Me3 mpba(4-) =N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)). After complete replacement of the Mg(II) ions within the coordination network and those hosted in the channels by either Co(II) or Ni(II) ions, 1 is transmetallated to yield two novel MOFs of formulae Co2 (II) {Co(II) 4 [Cu(II) 2 (Me3 mpba)2 ]3 }⋅56 H2 O (2) and Ni2 (II) {Ni(II) 4 [Cu(II) 2 (Me3 mpba)2 ]3 }⋅ 54 H2 O (3). This unique postsynthetic metal substitution affords materials with higher structural stability leading to enhanced gas sorption and magnetic properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Light funneling from a photonic crystal laser cavity to a nano-antenna: overcoming the diffraction limit in optical energy transfer down to the nanoscale.

PubMed

Mivelle, Mathieu; Viktorovitch, Pierre; Baida, Fadi I; El Eter, Ali; Xie, Zhihua; Vo, Than-Phong; Atie, Elie; Burr, Geoffrey W; Nedeljkovic, Dusan; Rauch, Jean-Yves; Callard, Ségolène; Grosjean, Thierry

2014-06-16

We show that the near-field coupling between a photonic crystal microlaser and a nano-antenna can enable hybrid photonic systems that are both physically compact (free from bulky optics) and efficient at transferring optical energy into the nano-antenna. Up to 19% of the laser power from a micron-scale photonic crystal laser cavity is experimentally transferred to a bowtie aperture nano-antenna (BNA) whose area is 400-fold smaller than the overall emission area of the microlaser. Instead of a direct deposition of the nano-antenna onto the photonic crystal, it is fabricated at the apex of a fiber tip to be accurately placed in the microlaser near-field. Such light funneling within a hybrid structure provides a path for overcoming the diffraction limit in optical energy transfer to the nanoscale and should thus open promising avenues in the nanoscale enhancement and confinement of light in compact architectures, impacting applications such as biosensing, optical trapping, local heating, spectroscopy, and nanoimaging.

High-pressure synthesis, crystal chemistry and physics of perovskites with small cations at the A site.

PubMed

Belik, Alexei A; Yi, Wei

2014-04-23

ABO3 perovskites with small cations at the A site (A = Sc(3+), In(3+) and Mn(2+) and B = Al(3+) and transition metals) are reviewed. They extend the corresponding families of perovskites with A(3+) = Y, La-Lu, and Bi and A(2+) = Cd, Ca, Sr and Ba and exhibit the largest structural distortions. As a result of these large distortions, they show, in many cases, distinct structural and magnetic properties. These are manifested in: B-site-ordered monoclinic structures of ScMnO3 and 'InMnO3'; an unusual superstructure of ScRhO3 and InRhO3; antiferromagnetic ground states and multiferroic properties of Sc2NiMnO6 and In2NiMnO6; two magnetic transitions in ScCrO3 and InCrO3 with very close transition temperatures; a Pnma-to-P-1 structural transition and k = (½, 0, ½) magnetic ordering in ScVO3; and incommensurate magnetic ordering of Mn(2+) spins in metallic MnVO3. A large number of simple ScBO3, InBO3 and MnBO3 perovskites has not been synthesized yet, and the number of experimental and theoretical works on each known ScBO3, InBO3 and MnBO3 perovskites counts to only one or two (except for ScAlO3). The synthesis, crystal chemistry and physics of perovskites with small cations at the A site is an emerging field in perovskite science.

Seismic anisotropy in the Earth's innermost inner core: Testing structural models against mineral physics predictions

DOE PAGES

Romanowicz, Barbara; Cao, Aimin; Godwal, Budhiram; ...

2016-01-06

Using an updated data set of ballistic PKIKP travel time data at antipodal distances, we test different models of anisotropy in the Earth's innermost inner core (IMIC) and obtain significantly better fits for a fast axis aligned with Earth's rotation axis, rather than a quasi-equatorial direction, as proposed recently. Reviewing recent results on the single crystal structure and elasticity of iron at core conditions, we find that an hcp structure with the fast c axis parallel to Earth's rotation is more likely but a body-centered cubic structure with the [111] axis aligned in that direction results in very similar predictionsmore » for seismic anisotropy. These models are therefore not distinguishable based on current seismological data. In addition, to match the seismological observations, the inferred strength of anisotropy in the IMIC (6–7%) implies almost perfect alignment of iron crystals, an intriguing, albeit unlikely situation, especially in the presence of heterogeneity, which calls for further studies. Fast axis of anisotropy in the central part of the inner core aligned with Earth's axis of rotation Lastly, the structure of iron in the inner core is most likely hcp, not bcc Not currently possible to distinguish between hcp and bcc structures from seismic observations« less

Synthesis and structure determination of uranyl peroxide nanospheres in the presence of organic structure directing agents

NASA Astrophysics Data System (ADS)

Forbes, T. Z.; Burns, P. C.

2007-12-01

Recently, actinyl peroxide nanoclusters containing 20, 24, 28, or 32 actinyl polyhedra have been synthesized and their structures identified with single crystal X-ray diffraction [1]. Most nanomaterials are composed of main group elements or transition metals, therefore, these actinyl nanospheres may display vastly different chemical and physical properties due to the presence of filled f-orbitals. A major goal of our research group is to create novel actinyl materials, focusing on nano- and mesoporous materials. The original nanosphere syntheses were limited to inorganic crystallization agents, such as monovalent cations. Over the last decade, the use of organic compounds and surfactants have received increased attention as structure-directing agents for the generation of novel inorganic materials. Using structure-directing organic amines we have successfully synthesized and determined the structures of uranyl nanospheres containing 40 and 50 uranyl polyhedra. The topology of the skeletal U-50 nanosphere is identical to the C50Cl10 fullerene [2]. The topographical relationship between the actinyl nanospheres and fullerene or fullerene-like material may provide additional insight into stable configurations for lower fullerenes. [1] Burns et al., Actinyl peroxide nanospheres. Angewandte Chemie, International Edition, 2005. 44(14): p. 2135. [2] Xie et al., Capturing the Labile Fullerene[50] as C50Cl10. Science, (2004) 305(5671): p. 699.

Likelihood-based modification of experimental crystal structure electron density maps

DOEpatents

Terwilliger, Thomas C [Sante Fe, NM

2005-04-16

A maximum-likelihood method for improves an electron density map of an experimental crystal structure. A likelihood of a set of structure factors {F.sub.h } is formed for the experimental crystal structure as (1) the likelihood of having obtained an observed set of structure factors {F.sub.h.sup.OBS } if structure factor set {F.sub.h } was correct, and (2) the likelihood that an electron density map resulting from {F.sub.h } is consistent with selected prior knowledge about the experimental crystal structure. The set of structure factors {F.sub.h } is then adjusted to maximize the likelihood of {F.sub.h } for the experimental crystal structure. An improved electron density map is constructed with the maximized structure factors.

Vapour phase growth and characterization of II-VI mixed crystals

NASA Astrophysics Data System (ADS)

Reddy, D. R.; Reddy, B. K.

1992-02-01

All II-VI semiconductors with melting temperatures well above 1000 degree(s)C and with appreciable congruent vaporization well below their melting temperatures leave little scope for any growth technique except for the slow but efficient vaporphase growth method. Theoretical flaw in diffusion models of vapor phase growth was corrected by Factor and Garrett by incorporating the flow velocity term which otherwise would lead to segregation of constituents. An additional degree of freedom arising from the presence of two components was well utilized to finely control the stoichiometry in binaries. In mixed II-VI systems the components are either three or four, depending on whether the system is a ternary or a quaternary. The added degrees of freedom make it very difficult to control stoichiometry. However, Igaki et al. demonstrated the feasibility of control of stoichiometry in CdSxSe1-x. In this paper, a self-sealing vaporphase growth technique used for both ternary and quaternary system is described. The systems studied are CdSxSe1-x, (ZnSe)x(CdTe)1-x and (ZnTe)x(CdSe)1-x. Results on growth mechanism, miscibility, structure, band gap variation, conductivity type variation with 'x' and transport properties are presented in a comparative way and discussed. CdSxSe1-x system in the entire 'X' has the same crystal structure and type of conductivity. The second system has the same zincblend structure but the type of conductivity is very sensitive to thermal treatment. In the last system both structure and types of conductivity are different. The discontinuities in properties associated with this divergent end compound are presented and discussed. Among the physical properties/parameters studied crystal structure, bandgap and nature of conductivity are tailorable, and magnitudes of conductivity and dielectric properties are very difficult to control in the crystals grown by this vapor phase method.

Copper Selenidophosphates Cu4P2Se6, Cu4P3Se4, Cu4P4Se3, and CuP2Se, Featuring Zero-, One-, and Two-Dimensional Anions.

PubMed

Kuhn, Alexander; Schoop, Leslie M; Eger, Roland; Moudrakovski, Igor; Schwarzmüller, Stefan; Duppel, Viola; Kremer, Reinhard K; Oeckler, Oliver; Lotsch, Bettina V

2016-08-15

Five new compounds in the Cu/P/Se phase diagram have been synthesized, and their crystal structures have been determined. The crystal structures of these compounds comprise four previously unreported zero-, one-, and two-dimensional selenidophosphate anions containing low-valent phosphorus. In addition to two new modifications of Cu4P2Se6 featuring the well-known hexaselenidohypodiphosphate(IV) ion, there are three copper selenidophosphates with low-valent P: Cu4P3Se4 contains two different new anions, (i) a monomeric (zero-dimensional) selenidophosphate anion [P2Se4](4-) and (ii) a one-dimensional selenidophosphate anion [Formula: see text], which is related to the well-known gray-Se-like [Formula: see text] Zintl anion. Cu4P4Se3 contains one-dimensional [Formula: see text] polyanions, whereas CuP2Se contains the 2D selenidophosphate [Formula: see text] polyanion. It consists of charge-neutral CuP2Se layers separated by a van der Waals gap which is very rare for a Zintl-type phase. Hence, besides black P, CuP2Se constitutes a new possible source of 2D oxidized phosphorus containing layers for intercalation or exfoliation experiments. Additionally, the electronic structures and some fundamental physical properties of the new compounds are reported. All compounds are semiconducting with indirect band gaps of the orders of around 1 eV. The phases reported here add to the structural diversity of chalcogenido phosphates. The structural variety of this family of compounds may translate into a variety of tunable physical properties.

Effect of binder liquid type on spherical crystallization.

PubMed

Maghsoodi, Maryam; Hajipour, Ali

2014-11-01

Spherical crystallization is a process of formation of agglomerates of crystals held together by binder liquid. This research focused on understanding the effect of type of solvents used as binder liquid on the agglomeration of crystals. Carbamazepine and ethanol/water were used respectively as a model drug and crystallization system. Eight solvents as binder liquid including chloroform, dichloromethane, isopropyl acetate, ethyl acetate, n-hexane, dimethyl aniline, benzene and toluene were examined to better understand the relationship between the physical properties of the binder liquid and its ability to bring about the formation of the agglomerates. Moreover, the agglomerates obtained from effective solvents as binder liquid were evaluated in term of size, apparent particle density and compressive strength. In this study the clear trend was observed experimentally in the agglomerate formation as a function of physical properties of the binder liquid such as miscibility with crystallization system. Furthermore, the properties of obtained agglomerates such as size, apparent particle density and compressive strength were directly related to physical properties of effective binder liquids. RESULTS of this study offer a useful starting point for a conceptual framework to guide the selection of solvent systems for spherical crystallization.

Precursor routes to quaternary intermetallics: Synthesis, crystal structure, and physical properties of clathrate-II Cs{sub 8}Na{sub 16}Al{sub 24}Si{sub 112}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Kaya; Dong, Yongkwan; Nolas, George S., E-mail: gnolas@usf.edu

A new quaternary clathrate–II composition, Cs{sub 8}Na{sub 16}Al{sub 24}Si{sub 112}, was synthesized by kinetically controlled thermal decomposition (KCTD) employing both NaSi and NaAlSi as the precursors and CsCl as a reactive flux. The crystal structure and composition of Cs{sub 8}Na{sub 16}Al{sub 24}Si{sub 112} were investigated using both Rietveld refinement and elemental analysis, and the temperature dependent transport properties were investigated. Our results indicate that KCTD with multiple precursors is an effective method for the synthesis of multinary inorganic phases that are not easily accessible by traditional solid-state synthesis or crystal growth techniques. - Graphical abstract: Quaternary Cs{sub 8}Na{sub 16}Al{sub 24}S{submore » 112} clathrate–II was synthesized for the first time by kinetically controlled thermal decomposition (KCTD) employing a NaSi+NaAlSi precursor mixture with CsCl as the reactive flux, and the structural and transport properties were investigated. Our approach demonstrates a new synthetic pathway for the synthesis of multinary inorganic compounds. This work reports the exploration of a new clathrate composition as this class of materials continues to be of interest for thermoelectrics and other energy-related applications.« less

Investigation on the path process of M doped ZnO (M = Gd, Mg) via the sol-gel method from dried gel to stable nanostructure powder

NASA Astrophysics Data System (ADS)

Suharno; Soegijono, B.; Budiawanti, S.; Fadillah, L.

2017-04-01

Doping is one of the effective methods to modify the physical properties of ZnO material in order to extend its applications. An investigation on Zn1-xMxO (M = Gd, Mg and x = 0.00, 0.03) nanopowders that have been synthesized by sol-gel method and sintered at 600 °C for 2 hours was reported. The decomposition process of the dried gel system was investigated by thermal gravimetric analysis (TGA) and the nanopowders with different heating temperature were studied using FT-IR spectroscopy. The crystal structure of the nanopowders after sintering at 600 °C was obtained using X-ray diffraction (XRD). The TGA curves of the samples showed the various weight loss regions corresponding to the removal of starting materials and no weight loss was observed in the temperature range of 300 to 800 °C which corresponded to the phase-crystallization step. The FTIR spectra showed that ZnO band was assigned to the stretching frequency at 669 cm-1 while Gd/Mg doped ZnO was at 668 cm-1 and 666 cm-1. From the XRD studies, the crystal structure of the samples indicated single phase ZnO crystalline and confirmed hexagonal wurtzite structure (space group of P63mc).

Modeling variability in dendritic ice crystal backscattering cross sections at millimeter wavelengths using a modified Rayleigh-Gans theory

NASA Astrophysics Data System (ADS)

Lu, Yinghui; Clothiaux, Eugene E.; Aydin, Kültegin; Botta, Giovanni; Verlinde, Johannes

2013-12-01

Using the Generalized Multi-particle Mie-method (GMM), Botta et al. (in this issue) [7] created a database of backscattering cross sections for 412 different ice crystal dendrites at X-, Ka- and W-band wavelengths for different incident angles. The Rayleigh-Gans theory, which accounts for interference effects but ignores interactions between different parts of an ice crystal, explains much, but not all, of the variability in the database of backscattering cross sections. Differences between it and the GMM range from -3.5 dB to +2.5 dB and are highly dependent on the incident angle. To explain the residual variability a physically intuitive iterative method was developed to estimate the internal electric field within an ice crystal that accounts for interactions between the neighboring regions within it. After modifying the Rayleigh-Gans theory using this estimated internal electric field, the difference between the estimated backscattering cross sections and those from the GMM method decreased to within 0.5 dB for most of the ice crystals. The largest percentage differences occur when the form factor from the Rayleigh-Gans theory is close to zero. Both interference effects and neighbor interactions are sensitive to the morphology of ice crystals. Improvements in ice-microphysical models are necessary to predict or diagnose internal structures within ice crystals to aid in more accurate interpretation of radar returns. Observations of the morphology of ice crystals are, in turn, necessary to guide the development of such ice-microphysical models and to better understand the statistical properties of ice crystal morphologies in different environmental conditions.

Polymer-Induced Heteronucleation for Protein Single Crystal Growth: Structural Elucidation of Bovine Liver Catalase and Concanavalin A Forms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foroughi, Leila M.; Kang, You-Na; Matzger, Adam J.

Obtaining single crystals for X-ray diffraction remains a major bottleneck in structural biology; when existing crystal growth methods fail to yield suitable crystals, often the target rather than the crystallization approach is reconsidered. Here we demonstrate that polymer-induced heteronucleation, a powerful technique that has been used for small molecule crystallization form discovery, can be applied to protein crystallization by optimizing the heteronucleant composition and crystallization formats for crystallizing a wide range of protein targets. Applying these advances to two benchmark proteins resulted in dramatically increased crystal size, enabling structure determination, for a half century old form of bovine liver catalasemore » (BLC) that had previously only been characterized by electron microscopy, and the discovery of two new forms of concanavalin A (conA) from the Jack bean and accompanying structural elucidation of one of these forms.« less

Laboratory plant study on the melting process of asbestos waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakai, Shinichi; Terazono, Atsushi; Takatsuki, Hiroshi

The melting process was studied as a method of changing asbestos into non-hazardous waste and recovering it as a reusable resource. In an initial effort, the thermal behaviors of asbestos waste in terms of physical and chemical structure have been studied. Then, 10 kg/h-scale laboratory plant experiments were carried out. By X-ray diffraction analysis, the thermal behaviors of sprayed-on asbestos waste revealed that chrysotile asbestos waste change in crystal structure at around 800 C, and becomes melted slag, mainly composed of magnesium silicate, at around 1,500 C. Laboratory plant experiments on the melting process of sprayed-on asbestos have shown thatmore » melted slag can be obtained. X-ray diffraction analysis of the melted slag revealed crystal structure change, and SEM analysis showed the slag to have a non-fibrous form. And more, TEM analysis proved the very high treatment efficiency of the process, that is, reduction of the asbestos content to 1/10{sup 6} as a weight basis. These analytical results indicate the effectiveness of the melting process for asbestos waste treatment.« less

Interactions of hyaluronan grafted on protein surfaces studied using a quartz crystal microbalance and a surface force balance.

PubMed

Jiang, Lei; Han, Juan; Yang, Limin; Ma, Hongchao; Huang, Bo

2015-10-07

Vocal folds are complex and multilayer-structured where the main layer is widely composed of hyaluronan (HA). The viscoelasticity of HA is key to voice production in the vocal fold as it affects the initiation and maintenance of phonation. In this study a simple layer-structured surface model was set up to mimic the structure of the vocal folds. The interactions between two opposing surfaces bearing HA were measured and characterised to analyse HA's response to the normal and shear compression at a stress level similar to that in the vocal fold. From the measurements of the quartz crystal microbalance, atomic force microscopy and the surface force balance, the osmotic pressure, normal interactions, elasticity change, volume fraction, refractive index and friction of both HA and the supporting protein layer were obtained. These findings may shed light on the physical mechanism of HA function in the vocal fold and the specific role of HA as an important component in the effective treatment of the vocal fold disease.

Physical Characterization of Orthorhombic AgInS2 Nanocrystalline Thin Films

NASA Astrophysics Data System (ADS)

El Zawawi, I. K.; Mahdy, Manal A.

2017-11-01

Nanocrystalline thin films of AgInS2 were synthesized using an inert gas condensation technique. The grazing incident in-plane x-ray diffraction technique was used to detect the crystal structure of the deposited and annealed thin films. The results confirmed that the as-deposited film shows an amorphous behavior and that the annealed film has a single phase crystallized in an orthorhombic structure. The orthorhombic structure and particle size were detected using high-resolution transmission electron microscopy. The particle size ( P_{{s}}) estimated from micrograph images of the nanocrystalline films were increased from 6 nm to 12 nm as the film thickness increased from 11 nm to 110 nm. Accordingly, increasing the film thickness up to 110 nm reflects varying the optical band gap from 2.75 eV to 2.1 eV. The photocurrent measurements were studied where the fast rise and decay of the photocurrent are governed by the recombination mechanism. The electrical conductivity behavior was demonstrated by two transition mechanisms: extrinsic transition for a low-temperature range (300-400 K) and intrinsic transition for the high-temperature region above 400 K.

Polyacrylonitrile nanofiber as polar solvent N,N-dimethyl formamide sensor based on quartz crystal microbalance technique

NASA Astrophysics Data System (ADS)

Rianjanu, A.; Julian, T.; Hidayat, S. N.; Suyono, E. A.; Kusumaatmaja, A.; Triyana, K.

2018-04-01

Here, we describe an N,N-dimethyl formamide (DMF) vapour sensor fabricated by coating polyacrylonitrile (PAN) nanofiber structured on quartz crystal microbalance (QCM). The PAN nanofiber sensors with an average diameter of 225 nm to 310 nm were fabricated via electrospinning process with different mass deposition on QCM substrate. The nanostructured of PAN nanofiber offers a high specific surface area that improved the sensing performance of nanofiber sensors. Benefiting from that fine structure, and high polymer-solvent affinity between PAN and DMF, the development of DMF sensors presented good response at ambient temperature. Since there is no chemical reaction between PAN nanofiber and DMF vapour, weak physical interaction such absorption and swelling were responsible for the sensing behavior. The results are indicating that the response of PAN nanofiber sensors has more dependency on the nanofiber structure (specific surface area) rather than its mass deposition. The sensor also showed good stability after a few days sensing. These findings have significant implications for developing DMF vapour sensor based on QCM coated polymer nanofibers.

Can pharmaceutical co-crystals provide an opportunity to modify the biological properties of drugs?

PubMed

Dalpiaz, Alessandro; Pavan, Barbara; Ferretti, Valeria

2017-08-01

Poorly soluble and/or permeable molecules jeopardize the discovery and development of innovative medicines. Pharmaceutical co-crystals, formed by an active pharmaceutical substance (API) and a co-crystal former, can show enhanced dissolution and permeation values compared with those of the parent crystalline pure phases. It is currently assumed that co-crystallization with pharmaceutical excipients does not affect the pharmacological activity of an API or, indeed, might even improve physical properties such as solubility and permeability. However, as we highlight here, the biological behavior of co-crystals can differ drastically with respect to that of their parent physical mixtures. Copyright © 2017 Elsevier Ltd. All rights reserved.

Engineering quadratic nonlinear photonic crystals for frequency conversion of lasers

NASA Astrophysics Data System (ADS)

Chen, Baoqin; Hong, Lihong; Hu, Chenyang; Zhang, Chao; Liu, Rongjuan; Li, Zhiyuan

2018-03-01

Nonlinear frequency conversion offers an effective way to extend the laser wavelength range. Quadratic nonlinear photonic crystals (NPCs) are artificial materials composed of domain-inversion structures whose sign of nonlinear coefficients are modulated with desire to implement quasi-phase matching (QPM) required for nonlinear frequency conversion. These structures can offer various reciprocal lattice vectors (RLVs) to compensate the phase-mismatching during the quadratic nonlinear optical processes, including second-harmonic generation (SHG), sum-frequency generation and the cascaded third-harmonic generation (THG). The modulation pattern of the nonlinear coefficients is flexible, which can be one-dimensional or two-dimensional (2D), be periodic, quasi-periodic, aperiodic, chirped, or super-periodic. As a result, these NPCs offer very flexible QPM scheme to satisfy various nonlinear optics and laser frequency conversion problems via design of the modulation patterns and RLV spectra. In particular, we introduce the electric poling technique for fabricating QPM structures, a simple effective nonlinear coefficient model for efficiently and precisely evaluating the performance of QPM structures, the concept of super-QPM and super-periodically poled lithium niobate for finely tuning nonlinear optical interactions, the design of 2D ellipse QPM NPC structures enabling continuous tunability of SHG in a broad bandwidth by simply changing the transport direction of pump light, and chirped QPM structures that exhibit broadband RLVs and allow for simultaneous radiation of broadband SHG, THG, HHG and thus coherent white laser from a single crystal. All these technical, theoretical, and physical studies on QPM NPCs can help to gain a deeper insight on the mechanisms, approaches, and routes for flexibly controlling the interaction of lasers with various QPM NPCs for high-efficiency frequency conversion and creation of novel lasers.

Topological framework for local structure analysis in condensed matter

PubMed Central

Lazar, Emanuel A.; Han, Jian; Srolovitz, David J.

2015-01-01

Physical systems are frequently modeled as sets of points in space, each representing the position of an atom, molecule, or mesoscale particle. As many properties of such systems depend on the underlying ordering of their constituent particles, understanding that structure is a primary objective of condensed matter research. Although perfect crystals are fully described by a set of translation and basis vectors, real-world materials are never perfect, as thermal vibrations and defects introduce significant deviation from ideal order. Meanwhile, liquids and glasses present yet more complexity. A complete understanding of structure thus remains a central, open problem. Here we propose a unified mathematical framework, based on the topology of the Voronoi cell of a particle, for classifying local structure in ordered and disordered systems that is powerful and practical. We explain the underlying reason why this topological description of local structure is better suited for structural analysis than continuous descriptions. We demonstrate the connection of this approach to the behavior of physical systems and explore how crystalline structure is compromised at elevated temperatures. We also illustrate potential applications to identifying defects in plastically deformed polycrystals at high temperatures, automating analysis of complex structures, and characterizing general disordered systems. PMID:26460045

Crystal structure of minoxidil at low temperature and polymorph prediction.

PubMed

Martín-Islán, Africa P; Martín-Ramos, Daniel; Sainz-Díaz, C Ignacio

2008-02-01

An experimental and theoretical investigation on crystal forms of the popular and ubiquitous pharmaceutical Minoxidil is presented here. A new crystallization method is presented for Minoxidil (6-(1-piperidinyl)-2,4-pyrimidinediamide 3-oxide) in ethanol-poly(ethylene glycol), yielding crystals with good quality. The crystal structure is determined at low temperature, with a final R value of 0.035, corresponding to space group P2(1) (monoclinic) with cell dimensions a = 9.357(1) A, b = 8.231(1) A, c = 12.931(2) A, and beta = 90.353(4) degrees . Theoretical calculations of the molecular structure of Minoxidil are set forward using empirical force fields and quantum-mechanical methods. A theoretical prediction for Minoxidil crystal structure shows many possible polymorphs. The predicted crystal structures are compared with X-ray experimental data obtained in our laboratory, and the experimental crystal form is found to be one of the lowest energy polymorphs.

Characterization of polypropylene–polyethylene blends by temperature rising elution and crystallization analysis fractionation

PubMed Central

del Hierro, Pilar

2010-01-01

The introduction of single-site catalysts in the polyolefins industry opens new routes to design resins with improved performance through multicatalyst-multireactor processes. Physical combination of various polyolefin types in a secondary extrusion process is also a common practice to achieve new products with improved properties. The new resins have complex structures, especially in terms of composition distribution, and their characterization is not always an easy task. Techniques like temperature rising elution fractionation (TREF) or crystallization analysis fractionation (CRYSTAF) are currently used to characterize the composition distribution of these resins. It has been shown that certain combinations of polyolefins may result in equivocal results if only TREF or CRYSTAF is used separately for their characterization. PMID:20730530

Mixed stack charge transfer crystals: Crossing the neutral-ionic borderline by chemical substitution

NASA Astrophysics Data System (ADS)

Castagnetti, Nicola; Masino, Matteo; Rizzoli, Corrado; Girlando, Alberto; Rovira, Concepció

2018-02-01

We report extensive structural and spectroscopic characterization of four mixed stack charge-transfer (ms-CT) crystals formed by the electron donor 3,3',5 ,5' -tetramethylbenzidine (TMB) with Chloranil (CA), Bromanil (BA), 2,5-difluoro-tetracyanoquinodimethane (TCNQF2), and tetrafluoro-tetracyanoquinodimethane (TCNQF4). Together with the separately studied TMB-TCNQ [Phys. Rev. B 95, 024101 (2017), 10.1103/PhysRevB.95.024101] the TMB-acceptor series spans a wide range of degree of CT, from about 0.14 to 0.91, crossing the neutral-ionic interface, yet retaining similar packing and donor-acceptor CT integrals. First principle calculations of key phenomenological parameters allow us to get insight into the factors determining the degree of CT and other relevant physical properties.

Probing Carrier Transport and Structure-Property Relationship of Highly Ordered Organic Semiconductors at the Two-Dimensional Limit.

PubMed

Zhang, Yuhan; Qiao, Jingsi; Gao, Si; Hu, Fengrui; He, Daowei; Wu, Bing; Yang, Ziyi; Xu, Bingchen; Li, Yun; Shi, Yi; Ji, Wei; Wang, Peng; Wang, Xiaoyong; Xiao, Min; Xu, Hangxun; Xu, Jian-Bin; Wang, Xinran

2016-01-08

One of the basic assumptions in organic field-effect transistors, the most fundamental device unit in organic electronics, is that charge transport occurs two dimensionally in the first few molecular layers near the dielectric interface. Although the mobility of bulk organic semiconductors has increased dramatically, direct probing of intrinsic charge transport in the two-dimensional limit has not been possible due to excessive disorders and traps in ultrathin organic thin films. Here, highly ordered single-crystalline mono- to tetralayer pentacene crystals are realized by van der Waals (vdW) epitaxy on hexagonal BN. We find that the charge transport is dominated by hopping in the first conductive layer, but transforms to bandlike in subsequent layers. Such an abrupt phase transition is attributed to strong modulation of the molecular packing by interfacial vdW interactions, as corroborated by quantitative structural characterization and density functional theory calculations. The structural modulation becomes negligible beyond the second conductive layer, leading to a mobility saturation thickness of only ∼3  nm. Highly ordered organic ultrathin films provide a platform for new physics and device structures (such as heterostructures and quantum wells) that are not possible in conventional bulk crystals.

Probing Carrier Transport and Structure-Property Relationship of Highly Ordered Organic Semiconductors at the Two-Dimensional Limit

NASA Astrophysics Data System (ADS)

Zhang, Yuhan; Qiao, Jingsi; Gao, Si; Hu, Fengrui; He, Daowei; Wu, Bing; Yang, Ziyi; Xu, Bingchen; Li, Yun; Shi, Yi; Ji, Wei; Wang, Peng; Wang, Xiaoyong; Xiao, Min; Xu, Hangxun; Xu, Jian-Bin; Wang, Xinran

2016-01-01

One of the basic assumptions in organic field-effect transistors, the most fundamental device unit in organic electronics, is that charge transport occurs two dimensionally in the first few molecular layers near the dielectric interface. Although the mobility of bulk organic semiconductors has increased dramatically, direct probing of intrinsic charge transport in the two-dimensional limit has not been possible due to excessive disorders and traps in ultrathin organic thin films. Here, highly ordered single-crystalline mono- to tetralayer pentacene crystals are realized by van der Waals (vdW) epitaxy on hexagonal BN. We find that the charge transport is dominated by hopping in the first conductive layer, but transforms to bandlike in subsequent layers. Such an abrupt phase transition is attributed to strong modulation of the molecular packing by interfacial vdW interactions, as corroborated by quantitative structural characterization and density functional theory calculations. The structural modulation becomes negligible beyond the second conductive layer, leading to a mobility saturation thickness of only ˜3 nm . Highly ordered organic ultrathin films provide a platform for new physics and device structures (such as heterostructures and quantum wells) that are not possible in conventional bulk crystals.

Theory and modeling of correlated ionic motions in hybrid organic-inorganic perovskites

NASA Astrophysics Data System (ADS)

Rappe, Andrew

The perovskite crystal structure hosts a wealth of intriguing properties, and the renaissance of interest in halide (and hybrid organic-inorganic) perovskites (HOIPs) has further broadened the palette of exciting physical phenomena. Breakthroughs in HOIP synthesis, characterization, and solar cell design have led to remarkable increases in reported photovoltaic efficiency. However, the observed long carrier lifetime and PV performance have eluded comprehensive physical justification. The hybrid perovskites serve as an enigmatic crossroads of physics. Concepts from crystalline band theory, molecular physics, liquids, and phase transitions have been applied with some success, but the observations of HOIPs make it clear that none of these conceptual frameworks completely fits. In this talk, recent theoretical progress in understanding HOIPs will be reviewed and integrated with experimental findings. The large amplitude motions of HOIPs will be highlighted, including ionic diffusion, anharmonic phonons, and dynamic incipient order on various length and time scales. The intricate relationships between correlated structural fluctuations, polar order, and excited charge carrier dynamics will also be discussed. This work was supported by the Office of Naval Research, under Grant N00014-14-1-0761.

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Yoreo, J; Orme, C; Dove, P

Since the dawn of life on earth, organisms have directed the crystallization of inorganic ions from solution to form minerals that meet specific biological needs. The resulting materials often exhibit remarkable properties, making the processes involved in biomineralization of interest to a wide array of scientific disciplines. From a geochemical standpoint, perhaps the most important consequence is that CaCO{sub 3} biomineral formation occurs in the Oceans on such a large scale that it influences many aspects of seawater chemistry and results in sequestration of carbon in the form of carbonate sediments. In this manner, the products of biomineralization are preservedmore » in the rock record and serve as an extensive chronicle of the interplay between biota and the earth system environment. From the point of view of materials synthesis, biological control over epitaxy is an elegant example of self-organization in complex molecular systems. Through selective introduction of peptides and proteins, living organisms deterministically modify nucleation, step kinetics, surface morphologies, and facet stabilities to produce nanophase materials, topologically complex single-crystals, and multi-layer composite. The resulting materials have biological functions as diverse as structural supports, porous filtration media, grinding and cutting tools, lenses, gravity sensors and magnetic guidance systems. As Table I shows, calcium carbonate minerals are ubiquitous amongst these biomineral structures. In addition , calcium carbonate is a well studied material that is easily crystallized and has known solution chemistry. Consequently, the calcium carbonate system provides an excellent model for investigating biomineralization processes. Surprisingly, in spite of the identification of carbonate biogenesis as a critical contributor to the carbon reservoir mediating climate change, and the enormous potential of biomimetic synthesis for production of tailored, crystalline nano- and micro-structured materials, the fundamental physical controls on carbonate biomineral formation remain poorly understood. Carbonates are formed in diverse environments almost exclusively by living organisms. These naturally occurring marine and fresh water minerals most commonly occur as the polymorphs of calcite, aragonite and vaterite which are nucleated and grown in the exoskeletons and tissues of marine and freshwater organisms ranging from simple bacteria and algae to crustaceans, molluscs, or sponges. It is known that the soluble fraction associated with mineralizing parts of organisms plays a primary role in crystal formation. In the formation of molluscan shells, this fraction is distinguished by the common presence of aspartic acid rich amino acid mixtures. It is also known that carbonates exposed to different polyamino acids exhibit different crystal habits. Belcher et al. showed that exposing growing CaCO{sub 3} crystals alternately to solutions containing polyanionic proteins associated with the aragonitic and calcitic layers of mollusc shells led to sequential switching of the crystal structure of the newly grown material between that of aragonite and calcite. Further work has demonstrated that these protein mixtures alter the morphology of the calcite growth surface and that they contain two fractions effecting growth: a step-binding fraction that inhibits step advancement on calcite surfaces, and a surface binding fraction that appears to lead to the subsequent nucleation of aragonite. Wierzbicki et al. found that polyaspartate molecules (ASP{sub 20}) bind to calcite surfaces. Finally, modeling of ASP{sub 15} binding to calcite planes predicts large binding energies for well defined orientations. This and related evidence shows that systematic relationships between crystal morphology and surface interactions with the reactive groups of the organic molecules must exist. However, the interplay between surface chemistry and the physical processes of nucleation and crystal growth are poorly understood because, until recently only ex situ biochemical studies focusing on the effect of changes in solution chemistry and/or surface stereo-chemistry on macroscopic crystal morphology had been performed.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ozkendir, Osman Murat, E-mail: ozkendir@gmail.com

Highlights: • Crystal and electronic structure properties of Nd{sub x}Ti{sub 1−x}BO{sub 2+d} structure were investigated. • New crystal structures for Nd–Ti complexes are determined. • Distortions in the crystal structure were observed as a result of Boron shortage. • Prominent change in electronic properties of the samples with the increasing Nd amount. - Abstract: Neodymium substituted TiBO{sub 3} samples were investigated according to their crystal, electric and electronic properties. Studies were conducted by X-ray absorption fine structure spectroscopy (XAFS) technique for the samples with different substitutions in the preparation processes. To achieve better crystal structure results during the study, XRDmore » pattern results were supported by extended-XAFS (EXAFS) analysis. The electronic structure analysis were studied by X-ray absorption near-edge structure spectroscopy (XANES) measurements at the room temperatures. Due to the substituted Nd atoms, prominent changes in crystal structure, new crystal geometries for Nd-Ti complexes, phase transitions in the crystals structure were detected according to the increasing Nd substitutions in the samples. In the entire stages of the substitutions, Nd atoms were observed as governing the whole phenomena due to their dominant characteristics in Ti geometries. Besides, electrical resistivity decay was determined in the materials with the increasing amount of Nd substitution.« less