Search

The discovery of twisted bilayer graphene with tunable superconductivity has diverted great focus at the world of twisted van der Waals heterostructures. Here we propose a paradigm for bilayer materials, where covalent bonding replaces the van der Waals interaction between the layers. On the example of germanene-stanene bilayer, we show that such systems demonstrate fascinating topological properties and manifest giant capacitance effects of the order of C = 102μ F as well as dipole-like charge densities of q = 1 − 2 × 10−4μ C cm−2, showing promise for 2D ferroelectricity. The observed unique behaviour is closely linked to transverse strain-induced buckling deformations at the bilayer/substrate interface. In alternative GeSn bilayer structures with low twist angles the strain distortions trigger rich topological defect physics. We propose that the GeSn bilayer topology may be switched locally by a substrate-strain-induced electric fields. We demonstrate an approach to fabricate covalent bilayer materials, holding vast possibilities to transform applications technologies across solar, energy and optoelectronic sectors.

Water dynamics in solutions with biological or non-biological solutes has been intensely studied when both components (solvent and solute) are amorphous. Here, we apply broadband dielectric spectroscopy combined with calorimetric measurements to analyze the dynamics of the aqueous solutions tri-propylene glycol (3PG) and ε-poly (lysine) (ε-PLL), after their water becomes semi-crystalline. Various crystallization levels were explored by conducting experiments with different annealing times at temperatures above the glass transition temperature (Tg). We find that the amount of ice depends on both the time and temperature of the annealing, and that this, in turn, affects Tg and dynamics of the amorphous part of the samples. However, it should be noted that the observed differences are relatively small for the degrees of crystallinity we have studied (up to about 26 wt% of the water). This also implies that the dynamic crossover of the water relaxation from a high temperature non-Arrhenius behavior to a low temperature Arrhenius dependence is unaffected by the partial crystallization and still occurs as a single crossover at the calorimetric Tg. Thus, we cannot detect two different crossovers, as commonly observed for other types of two-component systems, such as two glass formers., Financial support through the Grant Nos. PID2019-104650 GB-C21 (MICINN-Spain and FEDER-UE), LINKB20012 (CSIC), and IT1566-22 (Basque Government) are gratefully acknowledged, as well as the Grant No. 2019-04020 from the Swedish Research Council., We acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI).

Miltefosine (MLT,hexadecylphosphocholine (HePC)) is an alkylphospholipid (APL) clinically used against leishmaniasis and the topical treatment of cancer. Although the MLT mechanism of action has not yet been clarified, it is thought to be related to its incorporation into the plasma membrane, affecting lipid homeostasis. An essential feature of APLs is that they possess a lethal effect that acts only on malignant cells without affecting normal cells; this property indicates the potential selective antitumor properties of these types of drugs. However, the exact mechanism of APLs action at the molecular level is not yet known in detail. This study aimed to elucidate the molecular mechanisms of the interaction of the antitumor alkylphospholipid drug miltefosine with molecular models of normal and cancer cell membranes. The interaction of MLT with dipalmitoyl phosphatidylcholine (DPPC) multilamellar liposomes (MLVs) mimicking normal cell membrane and dipalmitoyl phosphatidylserine (DPPS) multilamellar liposomes (MLVs) mimicking cancer cell membrane was studied in the presence of (1 mol%,3 mol%, 6 mol%, 9 mol%, 15 mol%, 24 mol%, 30 mol% and 35 mol%) and in the absence of MLT by using two different non-invasive techniques; Fourier Transform Infrared (FTIR) spectroscopy and Differential Scanning Calorimetry (DSC). The comparative results show that miltefosine affects DPPS/MLT systems modeled cancer cells more than the DPPC/MLT system modeled healthy cells. Our results may be proof at the molecular level that miltefosine has selective antitumor properties. (c) 2022 Elsevier B.V. All rights reserved., Ege University Scientific Research Projects Coordination [FDK-2019-20901], This work was supported by Ege University Scientific Research Projects Coordination. (Project number is FDK-2019-20901) .

Stimuli-responsive microgel copolymer networks with ionizable functional groups have important applications for encapsulation of drugs, peptides, enzymes, proteins, or cells. Rational design of such networks can be based on characterization of stimuli-induced volume phase transition and spatial distribution of neutral and charged monomer units in crosslinked polymer chains. In this work we successfully synthesized poly(N-vinylcaprolactam-co-1-vinyl-3-methylimidazolium) (poly(VCL-VIM+)) microgels carrying permanent positive charges and demonstrate that H-1 high-resolution NMR spectroscopy in combination with transverse (T-2) magnetization relaxometry allows investigating separately the behavior of each functional group in the microgel network. The information about comonomer transition temperatures, width of transition, and change in transition entropy were reported and correlated with the concentration of charged functional groups and resulting electrophoretic mobility. A two-state approach was used to describe the temperature-induced volume phase transition separately for neutral and charged polymer segments. The core-corona architecture specific to each functional group was detected revealing that the charged methylated vinylimidazolium groups (VIM+) are concentrated mainly in the corona of the microgel. These biocompatible PVCL-based microgels functionalized with permanent positive charges are shown to serve as an antibacterial system against Gram-negative E. coli strains, due to the positive charge of the incorporated VIM+ comonomer in the polymer network.

Metal-halide perovskite semiconductors have attracted intense interest over the past decade, particularly for applications in photovoltaics. Low-energy optical phonons combined with significant crystal anharmonicity play an important role in charge-carrier cooling and scattering in these materials, strongly affecting their optoelectronic properties. We have observed optical phonons associated with Pb–I stretching in both MAPbI3 single crystals and polycrystalline thin films as a function of temperature by measuring their terahertz conductivity spectra with and without photoexcitation. An anomalous bond hardening was observed under above-bandgap illumination for both single-crystal and polycrystalline MAPbI3. First-principles calculations reproduced this photo-induced bond hardening and identified a related lattice contraction (photostriction), with the mechanism revealed as Pauli blocking. For single-crystal MAPbI3, phonon lifetimes were significantly longer and phonon frequencies shifted less with temperature, compared with polycrystalline MAPbI3. We attribute these differences to increased crystalline disorder, associated with grain boundaries and strain in the polycrystalline MAPbI3. Thus we provide fundamental insight into the photoexcitation and electron–phonon coupling in MAPbI3.

Conductance of the edge modes as well as conductance across the co-propagating edge modes around the \nu = 4/3, 5/3 and 2 quantum Hall states are measured by individually exciting the modes. Temperature dependent equilibration rates of the outer unity conductance edge mode are presented for different filling fractions. We find that the equilibration rate of the outer unity conductance mode at \nu = 2 is higher and more temperature sensitive compared to the mode at fractional filling 5/3 and 4/3. At lowest temperature, equilibration length of the outer unity conductance mode tends to saturate with lowering filling fraction \nu by increasing magnetic field B. We speculate this saturating nature of equilibration length is arising from an interplay of Coulomb correlation and spin orthogonality., Comment: 7 pages

High-performing thermoelectric materials such as Zn4Sb3and clathrates have atomic disorder as the root to their favorable properties. This makes it extremely difficult to understand and model their properties at a quantitative level, and thus effective structure–property relations are challenging to obtain. Cu2−xSe is an intensely studied, cheap and non-toxic high performance thermoelectric, which exhibits highly peculiar transport properties, especially near the β-to-α phase transition around 400 K, which must be related to the detailed nature of the crystal structure. Attempts to solve the crystal structure of the low-temperature phase, β-Cu2−xSe, have been unsuccessful since 1936. So far, all studies have assumed that β-Cu2−xSe has a three-dimensional periodic structure, but here we show that the structure is ordered only in two dimensions while it is disordered in the third dimension. Using the three-dimensional difference pair distribution function (3D-ΔPDF) analysis method for diffuse single-crystal X-ray scattering, the structure of the ordered layer is solved and it is shown that there are two modes of stacking disorder present which give rise to an average structure with higher symmetry. The present approach allows for a direct solution of structures with disorder in some dimensions and order in others, and can be thought of as a generalization of the crystallographic Patterson method. The local and extended structure of a solid determines its properties and Cu2−xSe represents an example of a high-performing thermoelectric material where the local atomic structure differs significantly from the average periodic structure observed from Bragg crystallography.

Herein we report silver(i) directed infinite coordination polymer network (ICPN) induced self-assembly of low molecular weight organic ligands leading to metallogelation. Structurally simple ligands are derived from 3-aminopyridine and 4-aminopyridine conjugates which are composed of either pyridine or 2,2'-bipyridine cores. The cation specific gelation was found to be independent of the counter anion, leading to highly entangled fibrillar networks facilitating the immobilization of solvent molecules. Rheological studies revealed that the elastic storage modulus (G') of a given gelator molecule is counter anion dependent. The metallogels derived from ligands containing a bipyridine core displayed higher G' values than those with a pyridine core. Furthermore, using single crystal X-ray diffraction studies and 1H-15N two-dimensional (2D) correlation NMR spectroscopy, we show that the tetracoordination of silver ions enables simultaneous coordination polymerization and metallosupramolecular cross-linking. The resulting metallogels show spontaneous, in situ nanoparticle (d < 2-3 nm) formation without any additional reducing agents. The silver nanoparticle formation was followed using spectroscopic studies, and the self-assembled fibrillar networks were imaged using transmission electron microscopy (TEM) imaging.

The dynamical evolution of an inhomogeneous ultracold atomic gas quenched at different controllable rates through the Bose-Einstein condensation phase transition is studied numerically in the premise of a recent experiment in an anisotropic harmonic trap. Our findings based on the stochastic (projected) Gross-Pitaevskii equation are shown to be consistent at early times with the predictions of the homogeneous Kibble-Zurek mechanism. This is demonstrated by collapsing the early dynamical evolution of densities, spectral functions and correlation lengths for different quench rates, based on an appropriate characterization of the distance to criticality felt by the quenched system. The subsequent long-time evolution, beyond the identified dynamical critical region, is also investigated by looking at the behaviour of the density wavefront evolution and the corresponding phase ordering dynamics.

Over the past decades, investigations of the anomalous low-energy electronic properties of ZrTe$_5$ have reached a wide array of conclusions. An open question is the growth method's impact on the stoichiometry of ZrTe$_5$ samples, especially given the very small density of states near its chemical potential. Here we report on high resolution scanning tunneling microscopy and spectroscopy measurements performed on samples grown via different methods. Using density functional theory calculations, we identify the most prevalent types of atomic defects on the surface of ZrTe$_5$, namely Te vacancies and intercalated Zr atoms. Finally, we precisely quantify their density and outline their role as ionized defects in the anomalous resistivity of this material., Comment: 12 pages, 10 figures; Accepted for publication in Physical Review Materials

We studied the electronic and vibrational properties of monazite-type SrCrO4 under compression. The study extended the pressure range of previous studies from 26 to 58 GPa. The existence of two previously reported phase transitions was confirmed at 9 and 14 GPa, and two new phase transitions were found at 35 and 48 GPa. These transitions involve several changes in the vibrational and transport properties with the new high-pressure phases having a conductivity lower than that of the previously known phases. No evidence of chemical decomposition or metallization of SrCrO4 was detected. A tentative explanation for the reported observations is discussed.

Aqueous solutions of a series of monodisperse poly(N-isopropylacrylamide)s end-labeled with n-butyl-1-pyrene at one or both chain ends (Py-n-PNIPAMs with n=1 or 2) were studied by turbidimetry, light scattering, and fluorescence. For a given polymer concentration and heating rate, the cloud point (T-c) of an aqueous Py-n-PNIPAM solution, determined by turbidimetry, was found to increase with the number-average molecular weight (M-n) of the polymer. The steady-state fluorescence spectra and time-resolved fluorescence decays of Py-n-PNIPAM aqueous solutions were analyzed and all parameters retrieved from these analyses were found to be affected as the solution temperature passed through T-c, the solution cloud point, and T-m, the temperature where dehydration of PNIPAM occurred. The trends obtained by fluorescence to characterize the aqueous Py-n-PNIPAM solutions as a function of temperature were found to be consistent with the model proposed for telechelic PNIPAM by Koga et al. in 2006. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 308-318

When controlling electronic properties of bulk materials, we usually assume that the basic crystal structure is fixed. However, in two-dimensional (2D) materials, atomic structure or to functionalize their properties. Various polymorphs can exist in transition metal dichalcogenides (TMDCs) from which 2D materials are generated, and polymorphism has drastic on the electronic states. Here we report the discovery of an polymorph is attracting growing interest as a controlling parameter unprecedented polymorph of a TMDC 2D material. By mechanical exfoliation, we made thin flakes from a single crystal of 2Ha-type tantalum disulfide (TaS2), a metallic TMDC with a charge-density-wave (CDW) phase. Microbeam X-ray diffraction measurements and electrical transport measurements indicate that thin flakes possess a polymorph different from any one known in TaS2 bulk crystals. Moreover, the flakes with the unique polymorph displayed the dramatically enhanced CDW ordering temperature. The present results suggest the potential existence of diverse structural and electronic phases accessible only in 2D materials.

Magnetic solid state cooling applications require families of samples where the magnetic transition is cascaded across the working range of the fridge. Although magnetic properties are widely studied, information relating to the mechanical properties of such systems is less prevalent. Here we study the mechanical properties of a series of magnetocaloric La(Co,Fe,Si)13 samples where the Co content is varied to produce a range of transition temperatures. It was found that at room temperature the flexural strength decreases and the Young's modulus increases with increasing Co content. Interestingly we find a significant reduction of Young's modulus at temperature around the magnetic transition temperature. This reduction was less pronounced with increasing Co content. We associate the softening with the magnetovolume coupling known to exist in these materials.

We report a family of ferroelectric materials which exhibit optical control of dielectric constant, polarization, and conductivity at ambient conditions. The evolution of photo-induced charge carriers under illumination of weak monochromatic light of wavelength λ = 405 nm developed electronic polarization that reorients or enhances the ionic polarization in the direction of the applied electric field, hence significantly increasing the net polarization. The presence of electronic polarization in perovskites, especially ABO3 oxides, and the contribution to the ionic polarization, is a matter of debate among ferroelectric community; however, recent experimental evidence proved that electronic polarization contributes to overall polarization in different ways: if it is additive, it will act along the direction of ionic polarization; and if it is subtractive, it will act in the opposite direction. We report a newly developed lead-based ferroelectric family Pb1-x(Li0.5Bi0.5)x(Zr0.2Ti0.8)O3 (PLBZT) for x = 0.3, 0.4, 0.5, which have been successfully synthesized by a conventional solid state reaction route. The X-ray diffraction patterns were recorded at room temperature and refined with Rietveld parameters which confirm its tetragonal structure with P4mm space group symmetry. The Raman spectra, dielectric properties and leakage currents are analyzed. The current conduction mechanisms obey bulk limited Poole–Frenkel model and provide optical dielectric constant similar to theoretical value to lead zirconate titanate. Publisher PDF

Monolayer transition metal dichalcogenides in the T' phase promise to realize the quantum spin Hall (QSH) effect at room temperature, because they exhibit a prominent spin-orbit gap between inverted bands in the bulk. Here we show that the binding energy of electron-hole pairs excited through this gap is larger than the gap itself in MoS2, a paradigmatic material that we investigate from first principles by many-body perturbation theory (MBPT). This paradoxical result hints at the instability of the T' phase against the spontaneous generation of excitons, and indeed we find that it gives rise to a recostructed `excitonic insulator' ground state. Importantly, we show that in this system topological and excitonic order cooperatively enhance the bulk gap by breaking the crystal inversion symmetry, in contrast to the case of bilayers where the frustration between the two orders is relieved by breaking time reversal symmetry. The excitonic topological insulator departs distinctively from the bare topological phase as it lifts the band spin degeneracy, which results in circular dichroism. A moderate biaxial strain applied to the system leads to two additional excitonic phases, different in their topological character but both ferroelectric as an effect of electron-electron interactions., Comment: five colour figures

Quantum spin Hall insulators make up a class of two-dimensional materials with a finite electronic band gap in the bulk and gapless helical edge states. In the presence of time-reversal symmetry, Z(2) topological order distinguishes the topological phase from the ordinary insulating one. Some of the phenomena that can be hosted in these materials, from one-dimensional low-dissipation electronic transport to spin filtering, could be promising for many technological applications in the fields of electronics, spintronics, and topological quantum computing. Nevertheless, the rarity of two-dimensional materials that can exhibit nontrivial Z(2) topological order at room temperature hinders development. Here, we screen a comprehensive database we recently identified of 1825 monolayers that can be exfoliated from experimentally known compounds to search for novel quantum spin Hall insulators. Using density-functional and many-body perturbation theory simulations, we identify 13 monolayers that are candidates for quantum spin Hall insulators including high-performing materials such as AsCuL2 and (platinum) jacutingaite (P2HgS3). We also identify monolayer Pd2HgSe3 (palladium jacutingaite) as a novel Kane-Mele quantum spin Hall insulator and compare it with platinum jacutingaite. A handful of promising materials are mechanically stable and exhibit Z(2) topological order, either unperturbed or driven by small amounts of strain. Such screening highlights a relative abundance of Z(2) topological order of around 1% and provides an optimal set of candidates for experimental efforts.

The family of 2D materials grows day by day, drastically expanding the scope of possible phenomena to be explored in two dimensions, as well as the possible van der Waals heterostructures that one can create. Such 2D materials currently cover a vast range of properties. Until recently, this family has been missing one crucial member - 2D magnets. The situation has changed over the last two years with the introduction of a variety of atomically-thin magnetic crystals. Here we will discuss the difference between magnetic states in 2D materials and in bulk crystals and present an overview of the 2D magnets that have been explored recently. We will focus, in particular, on the case of the two most studied systems - semiconducting CrI$_3$ and metallic Fe$_3$GeTe$_2$ - and illustrate the physical phenomena that have been observed. Special attention will be given to the range of novel van der Waals heterostructures that became possible with the appearance of 2D magnets, offering new perspectives in this rapidly expanding field.

The crystal structure of SnTe is investigated from 20 to 800 K in two samples with different carrier concentrations by single-crystal and powder synchrotron X-ray diffraction, coupled with maximum entropy analysis., SnTe is a promising thermoelectric and topological insulator material. Here, the presumably simple rock salt crystal structure of SnTe is studied comprehensively by means of high-resolution synchrotron single-crystal and powder X-ray diffraction from 20 to 800 K. Two samples with different carrier concentrations (sample A = high, sample B = low) have remarkably different atomic displacement parameters, especially at low temperatures. Both samples contain significant numbers of cation vacancies (1–2%) and ordering of Sn vacancies possibly occurs on warming, as corroborated by the appearance of multiple phases and strain above 400 K. The possible presence of disorder and anharmonicity is investigated in view of the low thermal conductivity of SnTe. Refinement of anharmonic Gram–Charlier parameters reveals marginal anharmonicity for sample A, whereas sample B exhibits anharmonic effects even at low temperature. For both samples, no indications are found of a low-temperature rhombohedral phase. Maximum entropy method (MEM) calculations are carried out, including nuclear-weighted X-ray MEM calculations (NXMEM). The atomic electron densities are spherical for sample A, whereas for sample B the Te electron density is elongated along the 〈100〉 direction, with the maximum being displaced from the lattice position at higher temperatures. Overall, the crystal structure of SnTe is found to be defective and sample-dependent, and therefore theoretical calculations of perfect rock salt structures are not expected to predict the properties of real materials.

The low-temperature phase-transition of silver oxide (Ag2O) has been investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy as a function of temperature. The thermal evolution of the local structure around Ag atoms has been determined. In particular, below the phase-transition temperature at ∼35 K, a progressive splitting of the Ag–Ag next-nearest-neighbor distances is observed. This definitely supports the idea that the phase-transition of Ag2O is due to displacive disorder of the Ag atoms.

The high pressure behaviors of the two perovskite structures (hexagonal 6H-SrIrO3 and orthorhombic 3C-SrIrO3) have been studied in diamond anvil cells to 43 and 60 GPa, respectively, using synchrotron powder X-ray diffraction. 6H-SrIrO3 was first synthesized at ambient pressure and subsequently transformed into 3C-SrIrO3 in a large volume press at 8.8 GPa and 1000 °C. Both polymorphs were found to retain the initial symmetry up to the highest pressures measured, but in the case of 6H-SrIrO3, two anomalies were identified: a change in the axial compressibilities at 24 GPa and a change in both the axial and volume compressibilities at 32 GPa. Fitting a 3rd order Birch-Murnaghan equation of state to the obtained P-V data yielded bulk moduli of K0=151.5(12) GPa (fitted range 0

Semiconductor charge transfer (CT) cocrystals are an emerging class of molecular materials which combines the characteristics of the constituent molecules in order to tune physical properties. Cocrystals can exhibit polymorphism, but different stoichiometries of the donor-acceptor (DA) pair can also give different structures. In addition, the structures of the donor and acceptor as pristine compounds can influence the resulting cocrystal forms. We report a structural study on several CT cocrystals obtained by combining the polyaromatic hydrocarbon perylene with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its fluorinated derivatives having increasing electronegativity. This is achieved by varying the amount of fluorine substitution on the aromatic ring, with TCNQ-F2 and TCNQ-F4. We find structures with different stoichiometries. Namely, the system perylene:TCNQ-F0 is found with ratios 1:1 and 3:1, while the systems perylene:TCNQ-Fx (x = 2, 4) are found with ratios 1:1 and 3:2. We discuss the structures on the basis of the polymorphism of perylene as pure compound, and show that by a judicious choice of growth temperature the crystal structure can be in principle designed a priori. We also analyze the structural motifs taking into account the degree of charge transfer between the perylene donor and the TCNQ-Fx acceptors and the optical gap determined from infrared (IR) spectroscopy. This family of materials exhibits tunable optical gaps in the near-IR (NIR), promising applications in organic optoelectronics.

A multiferroic composite consisting of single phases of 30 vol.% magnetostrictive ferrite and 70 vol.% relaxor ferroelectric has been synthesized. The ferrite exhibits a diffuse dielectric phase transition (DPT)with the transition temperature varying from 450 K to 600 K and an activation energy of 0.29 eV. Magnetically, it has a soft behavior with 70 emug−1 saturation magnetization and a Curie transition at ~620 K. The relaxor ferroelectric phase on the other hand exhibits two clear DPTs at 390 K–400 K and 150 K–300 K. The composite of these two shows a soft ferromagnetic behavior reminiscent of the ferrite along with 3 DPTs. There is strong coupling between the two orders – magnetostrictive and piezoelectric in the composite. The capacitance decreases by 45% in the presence of magnetic field corresponding to a sensitivity of 0.9% kOe−1, an extremely large value. The magnetoelectric coupling constant is found to be 20.6 mVcm−1Oe−1, a large value for a bulk composite. Microwave band stop filters of different thicknesses made from the composite have resonant frequencies which upshift in the presence of magnetic field indicating a multiferroic behavior with possibility for electric field tuning of resonant frequency.

© 2018, © 2018 Informa UK Limited, trading as Taylor & Francis Group. We confine a colloidal liquid crystal between parallel plates separated down to several times the rod length. By connecting the system to a reservoir we effectively create a grand canonical system, in which the liquid crystal displays an isotropic phase in the reservoir, but upon strong confinement becomes nematic between the parallel plates. This capillary nematisation transition can be followed down to the single particle level by means of laser scanning confocal microscopy. We compare the experimental findings to density functional theories (DFTs), within the Zwanzig model as well as a more advanced DFT, in which the effect of rod flexibility is taken into account. ispartof: Molecular Physics vol:116 issue:21-22 pages:2864-2871 status: published

Three-dimensional topological (crystalline) insulators are materials with an insulating bulk, but conducting surface states which are topologically protected by time-reversal (or spatial) symmetries. Here, we extend the notion of three-dimensional topological insulators to systems that host no gapless surface states, but exhibit topologically protected gapless hinge states. Their topological character is protected by spatio-temporal symmetries, of which we present two cases: (1) Chiral higher-order topological insulators protected by the combination of time-reversal and a four-fold rotation symmetry. Their hinge states are chiral modes and the bulk topology is $\mathbb{Z}_2$-classified. (2) Helical higher-order topological insulators protected by time-reversal and mirror symmetries. Their hinge states come in Kramers pairs and the bulk topology is $\mathbb{Z}$-classified. We provide the topological invariants for both cases. Furthermore we show that SnTe as well as surface-modified Bi$_2$TeI, BiSe, and BiTe are helical higher-order topological insulators and propose a realistic experimental setup to detect the hinge states., 8 pages (4 figures) and 16 pages supplemental material (7 figures)

The dislocation-mediated quantum melting of solids into quantum liquid crystals is extended from two to three spatial dimensions, using a generalization of boson-vortex or Abelian-Higgs duality. Dislocations are now Burgers-vector-valued strings that trace out worldsheets in spacetime while the phonons of the solid dualize into two-form (Kalb-Ramond) gauge fields. We propose an effective dual Higgs potential that allows for restoring translational symmetry in either one, two or three directions, leading to the quantum analogues of columnar, smectic or nematic liquid crystals. In these phases, transverse phonons turn into gapped, propagating modes while compressional stress remains massless. Rotational Goldstone modes emerge whenever translational symmetry is restored. We also consider electrically charged matter, and find amongst others that as a hard principle only two out of the possible three rotational Goldstone modes are observable using electromagnetic means., RevTex, 55 pages, 14 figures

Mixed micelle formation between two oppositely charged diblock copolymers that have a common thermosensitive nonionic block of poly(N-isopropylacrylamide) (PNIPAAM) has been studied. The block copolymer mixed solutions were investigated under equimolar charge conditions as a function of both temperature and total polymer concentrations by turbidimetry, differential scanning calorimetry, two-dimensional proton nuclear magnetic nuclear Overhauser effect spectroscopy (2D H-1 NMR NOESY), dynamic light scattering, and small angle X-ray scattering measurements. Well-defined and electroneutral cylindrical micelles were formed with a radius and a length of about 3 nm and 35 nm, respectively. In the micelles, the charged blocks built up a core, which was surrounded by a corona of PNIPAAM chains. The 2D H-1 NMR NOESY experiments showed that a minor block mixing occurred between the core blocks and the PNIPAAM blocks. By approaching the lower critical solution temperature of PNIPAAM, the PNIPAAM chains collapsed, which induced aggregation of the micelles. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1457-1469

The new molecular salt [1H]Br (1 = 4-amino-cinnamic acid) was obtained in two polymorphic modifications, forms A and B. While mechanical stress induces transformation of form A into form B, an unexpected effect of UV irradiation is observed on form A, i.e., a single crystal to single crystal (SCSC) transformation to a third polymorph, form C. Form B, on the contrary, responds to UV irradiation by undergoing a stepwise SCSC [2 + 2] photodimerization to α-[12H2]Br2, via formation of a solid state solutions in the whole compositional range. All transformations were followed by a combination of solid-state techniques, i.e., single crystal and powder X-ray diffraction, FTIR, and FT-Raman, and by solution 1H NMR. All structural changes also resulted in variations in crystal morphology/texture, and these were monitored via SEM analysis.

The competition between the length scales associated with the periodicity of a lattice potential and the cyclotron radius of a uniform magnetic field is known to have dramatic effects on the single-particle properties of a quantum particle, e.g., the fractal spectrum is known as the Hofstadter butterfly. Having this intricate competition in mind, we consider a two-component Fermi gas on a square optical lattice with opposite synthetic magnetic fields for the components, and study its effects on the many-body BCS-pairing phenomenon. By a careful addressing of the distinct superfluid transitions from the semi-metal, quantum spin-Hall insulator or normal phases, we explore the low-temperature phase diagrams of the model, displaying lobe structures that are reminiscent of the well-known Mott-insulator transitions of the Bose-Hubbard model., Comment: 5 pages with 4 figures in the Main text, and 3 additional figures Online. To appear in Phys. Rev. Lett

Nanoindentation-induced polar properties in (0 0 1)-oriented SrTiO3 single crystals were analysed using piezoresponse force microscopy and local Raman spectroscopy measurements. The area directly beneath the indenter showed a strong piezoelectric response, together with an enhanced response in the area along the direction tangential to the residual indent. Stress-induced stable polarization states near the crack areas were also observed. Local poling performed on the strained areas suggests a possibility of polarization reversal and the stability of field-induced polar states. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

LaSb2 has a layered crystal structure along the c-axis with ∼2% difference between the in-plane orthorombic a and b axes. Here, we report on the thermal conductivity, electrical resistivity, and Seebeck coefficient from 10 to 300 K as well as the magnetoresistance at 10 K. Using the van der Pauw technique on single crystal samples, the in-plane electrical resistivity tensor has been measured and it is found to be isotropic. An anisotropic crystal structure may have isotropic properties, but in the present case, the isotropic nature stems from crystal imperfection. Single crystal X-ray diffraction provides evidence of a mixing of the in-plane a- and b-directions leading to observed diffraction intensity where systematic absences are expected. Whether the underlying structural mechanism is twinning or stacking faults is unknown, but it could be the origin of the previously observed charge density wave states, and it may also explain the high unsaturating linear magnetoresistance reported here. At ambient conditions, LaSb2 is found to be stable in air, with no sign of bulk degradation after 5 years of storage; however, some change is observed in the amorphous background scattering.

We study the fate of the surface states of Bi$_2$Se$_3$ under disorder with strength larger than the bulk gap, caused by neon sputtering and nonmagnetic adsorbates. We find that neon sputtering introduces strong but dilute defects, which can be modeled by a unitary impurity distribution, whereas adsorbates, such as water vapor or carbon monoxide, are best described by Gaussian disorder. Remarkably, these two disorder types have a dramatically different effect on the surface states. Our soft x-ray ARPES measurements combined with numerical simulations show that unitary surface disorder pushes the Dirac state to inward quintuplet layers, burying it below an insulating surface layer. As a consequence, the surface spectral function becomes weaker, but retains its quasiparticle peak. This is in contrast to Gaussian disorder, which smears out the quasiparticle peak completely. At the surface of Bi$_2$Se$_3$, the effects of Gaussian disorder can be reduced by removing surface adsorbates using neon sputtering, which, however, introduces unitary scatterers. Since unitary disorder has a weaker effect than Gaussian disorder, the ARPES signal of the Dirac surface state becomes sharper upon sputtering., Comment: 5+2 pages. 4 figures

The nominal BaTiO3 compound often exhibits an assortment of controversial magnetic signals which can be simply explained through minute presence of spurious magnetic elements in the perovskite matrix, even when this compound is synthesized from high grade Ba and Ti precursors. Proton Induced X-Ray Emission (PIXE) technique enable to confirm similar to 100 ppm of Fe contaminant which masks the utterly BaTiO3 diamagnetism. Nevertheless, besides the expected paramagnetism of highly diluted Fe ions, it is also possible to observe a cooperative magnetic moment signature which exhibits an intricate relation with the phase transitions of the BaTiO3 matrix. Such magneto-electric coupling signature is further corroborated by Raman spectroscopy, dielectric and X-ray diffraction measurements, indicating to a partial segregation of a rich Fe oxide phase, having a local structure clamped to the perovskite crystallites, hence acting as a practical probe sensitive to the local structural transitions of the host material. (C) 2015 Elsevier B.V. All rights reserved.

Dielectric spectroscopy is employed to probe the frequency-dependent conductivity and dipolar dielectric response of solid C60Br6. Below approximately 215 K, charge conduction is electronic and well described by Mott's variable-range polaron hopping model, with effective hopping activation energy Ea varying between 0.12 eV at 125 K and 0.16 eV at 220 K, and most probable hopping range varying between 100 and 125% of the decay length of the localized polaron's wavefunction. Above 215 K a new contribution appears in the conductivity, accompanied by a weak endothermic feature in the calorimetric thermogram, which might signal a solid-solid phase transition. A broad dielectric loss feature is observed in the imaginary part of the permittivity. Such feature stems largely from a conductivity-related frequency-dependent loss associated with polaron hopping, as confirmed by the validity of the Barton-Nakajima-Namikawa condition. (C) 2016 Elsevier B.V. All rights reserved.

We compute the transport coefficients, namely, the coefficients of shear and bulk viscosity as well as thermal conductivity for hot and dense quark matter. The calculations are performed within the Nambu- Jona Lasinio (NJL) model. The estimation of the transport coefficients is made using a quasiparticle approach of solving the Boltzmann kinetic equation within the relaxation time approximation. The transition rates are calculated in a manifestly covariant manner to estimate the thermal-averaged cross sections for quark-quark and quark-antiquark scattering. The calculations are performed for finite chemical potential also. Within the parameters of the model, the ratio of shear viscosity to entropy density has a minimum at the Mott transition temperature. At vanishing chemical potential, the ratio of bulk viscosity to entropy density, on the other hand, decreases with temperature with a sharp decrease near the critical temperature, and vanishes beyond it. At finite chemical potential, however, it increases slowly with temperature beyond the Mott temperature. The coefficient of thermal conductivity also shows a minimum at the critical temperature., Comment: 24 pages, 10 Figures, discussions added, version to appear in Physical Review D

We discuss recent literature data on the relaxation times (the primary t(alpha)), viscosity, and self-diffusion in water-glycerol and water-methanol mixtures across a wide temperature range from the stable water phase to the deep supercooled regime (373-147K). In particular, to clarify the role of hydrophilicity interactions (the hydrogen bonds) and hydrophobic interactions we study the mixture in terms of the water molar fraction (X-W) with fixed temperatures at 5K steps across the entire composition range, and we find a marked deviation from the ideal thermodynamic behavior of the transport functions. This deviation is strongly T and X-W dependent and spans values that range from two orders of magnitude at the highest temperature to more than five in the deeply supercooled regime (more precisely, at similar or equal to 200K). We analyze these deviations in terms of how the measured values differ from ideal values and find that the hydrogen-bonding water network dominates system properties up to X-W = 0.3. We also examine an Arrhenius plot of the maximum excess value (Delta t(alpha)(T) vs. 1/T) and find two significant changes due to water: one at the dynamical crossover temperature (T-L similar or equal to 225K, i.e., the locus of the Widom line), and one at T similar or equal to 315K (the water isothermal compressibility chi(T) minimum).

Universal behavior of the magnetocaloric effect along with structural and critical exponent analysis in mixed manganite La0.67Ca0.33Mn1-xCrxO3 (x = 0.1, 0.25), [LCMCr0.1 and LCMCr0.25] exhibiting second order phase transition are investigated. Structural study using Reitveld refinement of XRD patterns indicates orthorhombic structure with Pnma space group. Modified Arrott plot method has been adopted to study the critical behavior of the compounds at their transition region, which gives values of beta = 0.555(6), gamma = 1.17(4) and delta = 2.7096(7) at T-C = 232.5 K for LCMCr0.1 and beta = 0.68 (1), gamma = 1.09(3) and delta = 2.9362(4) at T-C = 202.5 K for LCMCr0.25. The values are close to those expected for mean field ferromagnets with long range order. With increase in Cr content, the temperature corresponding to the maximum entropy change as well as the magnetic transition temperature gradually shifts to low temperatures. The maximum magnetic entropy change was found to be 3.5 J/kg K for x = 0.1 and 2.2 J/kg K for x = 0.25 for a field change of 5 T. The field dependence of the magnetic entropy change is also analyzed, which shows the power law dependence namely, Delta S-M alpha H-n, n = 0.9086(5) at T-C = 232.5 K and n = 0.849(7) at T-C = 202.5 K for LCMCr0.1 and LCMCr0.25 respectively. Relative cooling power was found to be about 147 J/kg for LCMCr0.1 and 88 J/kg for LCMCr0.25. The field dependence of the relative cooling power for both the compounds shows a H1+1/delta dependence with the delta values in agreement with the mean field model. (C) 2011 Elsevier Masson SAS. All rights reserved.

Dropping a Dimension? In most magnetic materials, the exchange interaction causes the spins on the neighboring sites of a crystal lattice to align. In the absence of exchange interactions, dipolar interactions, which are highly orientation dependent, are also expected to be able to cause magnetism. Kraemer et al. (p. 1416 ) present evidence for antiferromagnetism in a dipolar-coupled material, LiErF 4 . Although a three-dimensional system, its critical behavior was more reminiscent of a two-dimensional material.

The detrimental effects of repeated thermal/field cycling across the martensitic transition on the transport, magnetic and thermal properties of Ni(45)Co(5)Mn(38)Sb(12) are studied. With the help of resistivity and magnetization measurements, it is shown that the resistivity increases and the magnetization decreases monotonically with continuous temperature or field cycling across the martensitic transition. It is also found that the martensite to austenite transition temperature increases with repeated structural change. The changes occurring in these physical properties are seen to be irreversible in nature. The possible changes in the lattice and the microstructure by repeated structural change seem to be responsible for the observed variations. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The possibility of forming self-organized films using charge-stabilized dispersions of cellulose I nanofibrils and microgel beads of poly-(N-isopropylacrylamide-co-acrylic acid) copolymer is presented. The build-up behavior and the properties of the layer-by-layer (LbL)-constructed films were studied using quartz crystal microbalance with dissipation (QCM-D) and ellipsometry. The morphology of the formed films was also characterized using atomic force microscopy (AFM) imaging. The applied methods clearly demonstrated the successful LbL-assembly of the monodisperse microgels and nanofibrils. The in situ QCM-D measurements also revealed that contrary to the polyelectrolyte bound microgel particles, the nanofibrils-bound gel beads preserve their highly swollen state and do not suffer a partial collapse due to the lack of interdigitation of the oppositely charged components. To probe the accessibility of the gel beads in the formed films, the room temperature (similar to 25 degrees C) loading and release of a fluorescent dye (FITC) was also investigated. The incorporation of the cellulose nanofibrils into the multilayer resulted in an open structure that was found easily penetrable for the dye molecules even at constant room temperature, which is in sharp contrast with previously reported systems based on synthetic polyelectrolytes. The amount of dye released from the multilayer films could be fine-tuned with the number of bilayers. Finally, the thermoresponsivity of the films was also shown by triggering the burst release of the loaded dye when the film was collapsed. QC 20110321

The effect of pH on iron-containing complex coacervate core micelles [Fe(III)-C3Ms] is investigated in this paper. The Fe(III)-C3Ms are formed by mixing cationic poly(N-methyl-2-vinylpyridinium iodide)-b-poly(ethylene oxide) [P2MVP(41)-b-PEO(205)] and anionic iron coordination polymers [Fe(III)-L(2)EO(4)] at stoichiometric charge ratio. Light scattering and Cryo-TEM have been performed to study the variations of hydrodynamic radius and core structure with changing pH. The hydrodynamic radius of Fe(III)-C3Ms is determined mainly by the corona and does not change very much in a broad pH range. However, Cryo-TEM pictures and magnetic relaxation measurements indicate that the structure of the micellar cores changes upon changing the pH, with a more crystalline, elongated shape and lower relaxivity at high pH. We attribute this to the formation of mixed iron complexes in the core, involving both the bis-ligand and hydroxide ions. These complexes are stabilized toward precipitation by the diblock copolymer.

The present paper describes what happens at the surface of a crystal as its temperature steadily increases from zero Kelvin close to the bulk melting temperature. We treat thermal motion, such as the diffusion of individual adatoms establishing mass transport, the formation of adatom or vacancy gases coexisting with islands or steps of the condensed phase, surface phonons and the anharmonicity of the surface potential being markedly different from the one in bulk, as well as thermally induced reconstructions, surface roughening, and finally surface melting, which usually well precedes bulk melting. The paper intends to give an overview with references to the original and review literature.

Transparent glasses having molar composition (23-x)K{sub 2}O.xNa{sub 2}O.27Nb{sub 2}O{sub 5}.50SiO{sub 2} (x=0, 5, 10, 15 and 23) have been synthesized by the melt-quenching technique and their devitrification behaviour has been investigated by DTA and XRD. Depending on the composition, the glasses showed a glass transition temperature in the range 660-680 deg. C and devitrified in several steps. XRD measurements showed that the replacement of K{sub 2}O by Na{sub 2}O strongly affects the crystallization behaviour. Particularly, in the glasses with only potassium or low sodium content the first devitrification step is related to the crystallization of an unidentified phase, while in the glass containing only sodium, NaNbO{sub 3} crystallizes. For an intermediate sodium content (x=10 and 15) a potassium sodium niobate crystalline phase, belonging to the tungsten-bronze family, is formed by bulk nucleation. This system looks promising to produce active nanostructured glasses as the tungsten-bronze type crystals have ferroelectric, electro-optical and non-linear optical properties. Preliminary measurements evidenced SHG activity in the crystallized glasses containing this phase. - Graphical abstract: Synthesis of glasses (23-x)K{sub 2}O.xNa{sub 2}O.27Nb{sub 2}O{sub 5}.50SiO{sub 2} (x=0, 5, 10, 15 and 23) from which SHG active phases crystallize by bulk nucleation for non-linear optical nanostructured glasses.

We present an electron spectroscopy study of phase-pure AC(60) thin films (A = Rb, Cs) in their monomer (face-centred cubic (fcc)) and polymer phases. A surface electronic reconstruction is observed in polymeric RbC60, analogous to that reported for the fcc phase. As for pristine C-60, the occupied electronic states of AC(60) fullerides are not dramatically affected by polymerization. The energy separation between the leading feature in photoemission and inverse photoemission is similar in both stable AC(60) phases. These observations suggest that electron correlation effects are similar in the two phases, and that their different electronic behaviour is mainly related to the reduction of degeneracy of the polymer frontier states. Photoemission and electron-energy loss spectroscopy data show that the thin-film form of the RbC60 polymer is metallic at room temperature, and that it undergoes a metal-insulator transition at around 100 K. This transition temperature is much higher than that reported for the corresponding bulk phase and signals a poorer screening of Coulomb interactions at the film surface.

The (57)Fe Mossbauer spectroscopy of mononuclear [Fe(II)(isoxazole)(6)](ClO(4))(2) has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S = 0) and high-spin (S = 2) states.Temperature-dependent spin transition curves have been constructed with the least-square fitted data obtained from the Mossbauer spectra measured at various temperatures between 84 and 270 K during a cooling and heating cycle. This compound exhibits an unusual temperature-dependent spin transition behaviour with T(C)(down arrow) = 223 and T(C)(up arrow) = 213 K occurring in the reverse order in comparison to those observed in SQUID observation and many other spin transition compounds. The compound has three high-spin Fe(II) sites at the highest temperature of study of which two undergo spin transitions. The Compound seems to undergo a structural phase transition around the spin transition temperature, which plays a significant role in the spin crossover behaviour as well as the magnetic properties of the compound at temperatures below T(C). The present study reveals an increase in high-spin fraction upon hearing in the temperature range below T(C) and an explanation is provided. (C) 2008 Elsevier Ltd. All rights reserved.

We have studied the phase behavior of zwitterionic phospholipid dioleoylphosphatidylcholine (DOPC) vesicles (membranes) and interpreted our results using scaling arguments in combination with molecular realistic self-consistent field (SCF) calculations. DOPC membranes acquire a partial negative charge per lipid molecule at intermediate NaBr concentrations. As a result of this, dilute DOPC solutions form stable unilamellar vesicles. Both at low and high salt concentrations phase separation into a lamellar and a vesicular phase is observed. The vesicle radius decreases as a power law with decreasing lipid concentration. This power-law concentration dependence indicates that the vesicle phase is entropically stabilized; the size of the DOPC vesicles result from a competition between the bending energy and translation and undulation entropy. This scaling behavior breaks down for very small vesicles. This appears to be consistent with SCF predictions that point to the fact that in this regime the mean bending modulus kc increases with curvature. The SCF theory predicts that, at low ionic strength, the membrane stability improves when there is more charge on the lipids. Upon a decrease of the ionic strength, lipids with a full negative charge form vesicles that grow exponentially in size because the mean bending modulus increases with decreasing ionic strength. At the same time the Gaussian bending modulus becomes increasingly negative such that the overall bending energy tends to zero. This indicates that small micelles become the dominant species. The SCF theory thus predicts a catastrophic break down of giant vesicles in favor of small micelles at sufficiently low ionic strength and high charge density on the lipids.

Ian M. Reaney acknowledges the support of the National Institute of Standards and Technology Visiting Scientist program. Tetragonal Tungsten Bronzes (TTBs) - an important class of oxides known to exhibit ferroelectricity - undergo complex distortions, including rotations of oxygen octahedra, which give rise to either incommensurately or commensurately modulated superstructures. Many TTBs display broad, frequency-dependent relaxor dielectric behaviour rather than sharper frequency-independent normal ferroelectric anomalies but the exact reasons that favor a particular type of dielectric response for a given composition remain unclear. In this contribution the influence of incommensurate/commensurate displacive modulations on the onset of relaxor/ferroelectric behaviour in TTBs is assessed in the context of basic crystal-chemical factors, such as positional disorder, ionic radii and polarizabilities, and point defects. We present a predictive crystal-chemical model that rationalizes composition-structure-properties relations for a broad range of TTB systems. Postprint

A charge-density wave (CDW) state has a broken symmetry described by a complex order parameter with an amplitude and a phase. The conventional view, based on clean, weak-coupling systems, is that a finite amplitude and long-range phase coherence set in simultaneously at the CDW transition temperature T$_{cdw}$. Here we investigate, using photoemission, X-ray scattering and scanning tunneling microscopy, the canonical CDW compound 2H-NbSe$_2$ intercalated with Mn and Co, and show that the conventional view is untenable. We find that, either at high temperature or at large intercalation, CDW order becomes short-ranged with a well-defined amplitude that impacts the electronic dispersion, giving rise to an energy gap. The phase transition at T$_{cdw}$ marks the onset of long-range order with global phase coherence, leading to sharp electronic excitations. Our observations emphasize the importance of phase fluctuations in strongly coupled CDW systems and provide insights into the significance of phase incoherence in `pseudogap' states., main manuscript plus supplementary information

Transport properties of the charge ordering compound $\beta-$Na$_{0.33}$V$_2$O$_5$ are studied in the temperature range from 30 K to 300 K using current driven DC conductivity experiments. It is found that below the metal-insulator transition temperature (T$_{mi}$ = 136 K) this material shows a typical nonlinear charge density wave behavior. The observed conductivity is discussed in terms of a classical domain model for charge density wave transport., Comment: 8 pages, 9 figures, final version

The weak-field dielectric properties of ordered, disordered, and lead-deficient disordered Pb(Sc0.5Ta0.5)O-3 (PST) ceramics (PST-O, PST-D, and PST-DV, respectively) were investigated under various de-bias conditions. The de-bias field influences the paraelectric-to-ferroelectric transition in PST-O and the relaxor-to-normal-ferroelectric transition in disordered PST-D, Phase diagrams, with respect to de bias and temperature, were proposed for ordered and disordered PST materials. A field-induced ferroelectric state that originated from the residual non-ordered regions in PST-O was revealed by analyzing the Curie-Weiss behavior of the materials under bias. It is shown that, in PST-DV, a de bias cannot induce an abrupt ferroelectric-to-relaxor transition. A dielectric anomaly observed at low temperatures in all three types of PST materials is attributed to a poling process.