Fingerprints of Critical Phenomena in a Quantum Paraelectric Ensemble of Nanoconfined Water Molecules.

We have studied the radio frequency dielectric response of a system consisting of separate polar water molecules periodically arranged in nanocages formed by the crystal lattice of the gemstone beryl. Below T = 20-30 K, quantum effects start to dominate the properties of the electric dipolar system as manifested by a crossover between the Curie-Weiss and the Barrett regimes in the temperature-dependent real dielectric permittivity ε'(T). When analyzing in detail the temperature evolution of the reciprocal permittivity (ε')-1 down to T ≈ 0.3 K and comparing it with the data obtained for conventional quantum paraelectrics, like SrTiO3, KTaO3, we discovered clear signatures of a quantum-critical behavior of the interacting water molecular dipoles: Between T = 6 and 14 K, the reciprocal permittivity follows a quadratic temperature dependence and displays a shallow minimum below 3 K. This is the first observation of "dielectric fingerprints" of quantum-critical phenomena in a paraelectric system of coupled point electric dipoles.

Two Linear Regimes in Optical Conductivity of a Type-I Weyl Semimetal: The Case of Elemental Tellurium.

Employing high-pressure infrared spectroscopy we unveil the Weyl semimetal phase of elemental Te and its topological properties. The linear frequency dependence of the optical conductivity provides clear evidence for metallization of trigonal tellurium (Te-I) and the linear band dispersion above 3.0 GPa. This semimetallic Weyl phase can be tuned by increasing pressure further: a kink separates two linear regimes in the optical conductivity (at 3.7 GPa), a signature proposed for Type-II Weyl semimetals with tilted cones; this however reveals a different origin in trigonal tellurium. Our density-functional calculations do not reveal any significant tilting and suggest that Te-I remains in the Type-I Weyl phase, but with two valence bands in the vicinity of the Fermi level. Their interplay gives rise to the peculiar optical conductivity behavior with more than one linear regime. Pressure above 4.3 GPa stabilizes the more complex Te-II and Te-III polymorphs, which are robust metals.

Single-Gap Superconductivity and Dome of Superfluid Density in Nb-Doped SrTiO_{3}.

SrTiO_{3} exhibits a superconducting dome upon doping with Nb, with a maximum critical temperature T_{c}≈0.4 K. Using microwave stripline resonators at frequencies from 2 to 23 GHz and temperatures down to 0.02 K, we probe the low-energy optical response of superconducting SrTiO_{3} with a charge carrier concentration from 0.3 to 2.2×10^{20} cm^{-3}, covering the majority of the superconducting dome. We find single-gap electrodynamics even though several electronic bands are superconducting. This is explained by a single energy gap 2Δ due to gap homogenization over the Fermi surface consistent with the low level of defect scattering in Nb-doped SrTiO_{3}. Furthermore, we determine T_{c}, 2Δ, and the superfluid density as a function of charge carrier concentration, and all three quantities exhibit the characteristic dome shape.

On the depolarization in granular thin films: a Mueller-matrix approach.

We describe a general method to disclose the information hidden in Mueller matrices experimentally obtained from depolarizing samples. Although spectroscopic Mueller-matrix ellipsometry allows for a model-free characterization of inhomogeneous samples, i.e., independently from any assumption on the sample structure, the interpretation of the obtained results is often challenging. The proposed method combines three different decomposition techniques applied to the measured Mueller matrices in transmission and reflection of granular thin films with different thicknesses and densities. We demonstrate that the comparative analysis of the respective differential-, product-, and sum-decomposition of the Mueller matrices, together with correlation effects and the visualization as a Poincaré sphere, reveals the particular underlying physical processes of depolarization. As an example, we apply this method on granular BaSO4 thin films. This method is general and can be applied to a wide variety of intrinsically inhomogeneous materials with applications in physics, industry, biology, or medicine.

Europium-based iron pnictides: a unique laboratory for magnetism, superconductivity and structural effects.

Despite decades of intense research, the origin of high-temperature superconductivity in cuprates and iron-based compounds is still a mystery. Magnetism and superconductivity are traditionally antagonistic phenomena; nevertheless, there is basically no doubt left that unconventional superconductivity is closely linked to magnetism. But this is not the whole story; recently, also structural effects related to the so-called nematic phase gained considerable attention. In order to obtain more information about this peculiar interplay, systematic material research is one of the most important attempts, revealing from time to time unexpected effects. Europium-based iron pnictides are the latest example of such a completely paradigmatic material, as they display not only spin-density-wave and superconducting ground states, but also local Eu2+ magnetism at a similar temperature scale. Here we review recent experimental progress in determining the complex phase diagrams of europium-based iron pnictides. The conclusions drawn from the observations reach far beyond these model systems. Thus, although europium-based iron pnictides are very peculiar, they provide a unique platform to study the common interplay of structural-nematic, magnetic and electronic effects in high-temperature superconductors.

The classical and quantum dynamics of molecular spins on graphene.

Controlling the dynamics of spins on surfaces is pivotal to the design of spintronic and quantum computing devices. Proposed schemes involve the interaction of spins with graphene to enable surface-state spintronics and electrical spin manipulation. However, the influence of the graphene environment on the spin systems has yet to be unravelled. Here we explore the spin-graphene interaction by studying the classical and quantum dynamics of molecular magnets on graphene. Whereas the static spin response remains unaltered, the quantum spin dynamics and associated selection rules are profoundly modulated. The couplings to graphene phonons, to other spins, and to Dirac fermions are quantified using a newly developed model. Coupling to Dirac electrons introduces a dominant quantum relaxation channel that, by driving the spins over Villain's threshold, gives rise to fully coherent, resonant spin tunnelling. Our findings provide fundamental insight into the interaction between spins and graphene, establishing the basis for electrical spin manipulation in graphene nanodevices.

Physical interpretation of Mueller matrix spectra: a versatile method applied to gold gratings.

The interaction of nanostructures, periodic or random, with polarized light creates very rich physics where scattering, diffraction and absorbance are linked to a variety of dispersive modes and coupling effects. Each of these excitations depends strongly on polarization, angle of incidence, azimuthal orientation of the sample and wavelength. The entire optical response can be obtained, independently from any model, by measuring the Mueller matrices at various k-vectors over a broad frequency range. This results in complex data hiding the underlying physics. Here we present a simple but versatile method to identify the physical properties present in the Mueller matrices. This method is applicable to a wide variety of photonic and plasmonic samples. Based on the simple example of a one-dimensional gold grating where the optical response is characterized not only by diffraction but also by a complex mixing of polarization, we present a very general procedure to analyze the Mueller matrix data using simple analytical tools. The calculated Mueller matrix contour plots obtained from an effective anisotropic layer model are completed by the presence of plasmonic modes, Rayleigh-Woods anomalies and the interband transition absorbance. A comparison of the so-constructed contour plots with the measured ones satisfactorily connects the optical properties of the grating to their physical origin. This straightforward procedure is very general and will be powerful for the analysis of complex optical nanostructures.

The metal-insulator transition in the organic conductor ß″-(BEDT-TTF)2Hg(SCN)2Cl.

We explore the nature of the metal-insulator transition in the two-dimensional organic compound ß″-(BEDT-TTF)2Hg(SCN)2Cl by x-ray, electrical transport, ESR, Raman, and infrared investigations. Magnetic and vibrational spectroscopy concurrently reveal a gradual dimerization along the stacking direction (a-b), setting in already at the crossover temperature of 150 K from the metallic to the insulating state. A spin gap of Δσ=47 meV is extracted. From the activated resistivity behavior below T = 55 K, a charge gap of Δρ=60 meV is derived. At TCO = 72 K, the C=C vibrational modes reveal the development of a charge-ordered state with a charge disproportionation of 2δρ=0.34e. In addition to a slight structural dimerization, charge-order causes stripes most likely perpendicular to the stacks.

Depolarization of a randomly distributed plasmonic meander metasurface characterized by Mueller matrix spectroscopic ellipsometry.

Metallic nanostructures offer efficient solutions in polarization control with a very low thickness. In this report, we investigate the optical properties of a nano-fabricated plasmonic pseudo-depolarizer using Mueller matrix spectroscopic ellipsometry in transmission configuration. The depolarizer is composed of 256 square cells, each containing a periodically corrugated metallic film with random orientation. The full Mueller matrix was analyzed as a function of incident angle in a range between 0 and 20° and over the whole rotation angle range. Depolarization could be achieved in two visible wavelength regions around the short-range and long-range surface plasmon polariton frequencies, respectively. Furthermore, depolarization for circularly polarized light was 2.5 times stronger than that for linearly polarized light. Our results could work as a guidance for realizing a broadband high efficiency dielectric metasurface depolarizers.

Universal sheet resistance and revised phase diagram of the cuprate high-temperature superconductors.

Upon introducing charge carriers into the copper-oxygen sheets of the enigmatic lamellar cuprates, the ground state evolves from an insulator to a superconductor and eventually to a seemingly conventional metal (a Fermi liquid). Much has remained elusive about the nature of this evolution and about the peculiar metallic state at intermediate hole-carrier concentrations (p). The planar resistivity of this unconventional metal exhibits a linear temperature dependence (ρ ∝ T) that is disrupted upon cooling toward the superconducting state by the opening of a partial gap (the pseudogap) on the Fermi surface. Here, we first demonstrate for the quintessential compound HgBa2CuO4+δ a dramatic switch from linear to purely quadratic (Fermi liquid-like, ρ ∝ T(2)) resistive behavior in the pseudogap regime. Despite the considerable variation in crystal structures and disorder among different compounds, our result together with prior work gives insight into the p-T phase diagram and reveals the fundamental resistance per copper-oxygen sheet in both linear (ρ = A1T) and quadratic (ρ = A2T(2)) regimes, with A1 ∝ A2 ∝ 1/p. Theoretical models can now be benchmarked against this remarkably simple universal behavior. Deviations from this underlying behavior can be expected to lead to new insight into the nonuniversal features exhibited by certain compounds.

Direct Observation of Very Large Zero-Field Splitting in a Tetrahedral Ni(II)Se4 Coordination Complex.

The high-spin (S = 1) tetrahedral Ni(II) complex [Ni{(i)Pr2P(Se)NP(Se)(i)Pr2}2] was investigated by magnetometry, spectroscopic, and quantum chemical methods. Angle-resolved magnetometry studies revealed the orientation of the magnetization principal axes. The very large zero-field splitting (zfs), D = 45.40(2) cm(-1), E = 1.91(2) cm(-1), of the complex was accurately determined by far-infrared magnetic spectroscopy, directly observing transitions between the spin sublevels of the triplet ground state. These are the largest zfs values ever determined--directly--for a high-spin Ni(II) complex. Ab initio calculations further probed the electronic structure of the system, elucidating the factors controlling the sign and magnitude of D. The latter is dominated by spin-orbit coupling contributions of the Ni ions, whereas the corresponding effects of the Se atoms are remarkably smaller.

Dynamic control of magnetic nanowires by light-induced domain-wall kickoffs.

Controlling the speed at which systems evolve is a challenge shared by all disciplines, and otherwise unrelated areas use common theoretical frameworks towards this goal. A particularly widespread model is Glauber dynamics, which describes the time evolution of the Ising model and can be applied to any binary system. Here we show, using molecular nanowires under irradiation, that Glauber dynamics can be controlled by a novel domain-wall kickoff mechanism. In contrast to known processes, the kickoff has unambiguous fingerprints, slowing down the spin-flip attempt rate by several orders of magnitude, and following a scaling law. The required irradiance is very low, a substantial improvement over present methods of magneto-optical switching. These results provide a new way to control and study stochastic dynamic processes. Being general for Glauber dynamics, they can be extended to different kinds of magnetic nanowires and to numerous fields, ranging from social evolution to neural networks and chemical reactivity.

Characterization of the quasi-one-dimensional compounds δ-(EDT-TTF-CONMe2)2X, X=AsF6 and Br by vibrational spectroscopy and density functional theory calculations.

We have investigated the infrared spectra of the quarter-filled charge-ordered insulators δ-(EDT-TTF-CONMe2)2X (X= AsF6, Br) along all three crystallographic directions in the temperature range from 300 to 10 K. DFT-assisted normal mode analysis of the neutral and ionic EDT-TTF-CONMe2 molecule allows us to assign the experimentally observed intramolecular modes and to obtain relevant information on the charge ordering and intramolecular interactions. From frequencies of charge-sensitive vibrations we deduce that the charge-ordered state is already present at room temperature and does not change on cooling, in agreement with previous NMR measurements. The spectra taken along the stacking direction clearly show features of vibrational overtones excited due to the anharmonic electronic molecule potential caused by the large charge disproportionation between the molecular sites. The shift of certain vibrational modes indicates the onset of the structural transition below 200 K.

Evolution of ferroelectricity in tetrathiafulvalene-p-chloranil as a function of pressure and temperature.

The neutral-to-ionic phase transition in the mixed-stack charge-transfer complex tetrathiafulvalene-p-chloranil (TTF-CA) has been studied by pressure-dependent infrared spectroscopy up to p = 11 kbar and down to low temperatures, T = 10 K. By tracking the C=O antisymmetric stretching mode of CA molecules, we accurately determine the ionicity of TTF-CA in the pressure-temperature phase diagram. At any point, the TTF-CA crystal bears only a single ionicity; there is no coexistence region or an exotic high-pressure phase. Our findings shed new light on the role of electron-phonon interaction in the neutral-ionic transition.

Vibrational states of a water molecule in a nano-cavity of beryl crystal lattice.

Low-energy excitations of a single water molecule are studied when confined within a nano-size cavity formed by the ionic crystal lattice. Optical spectra are measured of manganese doped beryl single crystal Mn:Be3Al2Si6O18, that contains water molecules individually isolated in 0.51 nm diameter voids within the crystal lattice. Two types of orientation are distinguished: water-I molecules have their dipole moments aligned perpendicular to the c axis and dipole moments of water-II molecules are parallel to the c-axis. The optical conductivity σ(ν) and permittivity ɛ'(ν) spectra are recorded in terahertz and infrared ranges, at frequencies from several wavenumbers up to ν = 7000 cm(-1), at temperatures 5-300 K and for two polarizations, when the electric vector E of the radiation is parallel and perpendicular to the c-axis. Comparative experiments on as-grown and on dehydrated samples allow to identify the spectra of σ(ν) and ɛ'(ν) caused exclusively by water molecules. In the infrared range, well-known internal modes ν1, ν2, and ν3 of the H2O molecule are observed for both polarizations, indicating the presence of water-I and water-II molecules in the crystal. Spectra recorded below 1000 cm(-1) reveal a rich set of highly anisotropic features in the low-energy response of H2O molecule in a crystalline nano-cavity. While for E∥c only two absorption peaks are detected, at ~90 cm(-1) and ~160 cm(-1), several absorption bands are discovered for E⊥c, each consisting of narrower resonances. The bands are assigned to librational (400-500 cm(-1)) and translational (150-200 cm(-1)) vibrations of water-I molecule that is weakly coupled to the nano-cavity "walls." A model is presented that explains the "fine structure" of the bands by a splitting of the energy levels due to quantum tunneling between the minima in a six-well potential relief felt by a molecule within the cavity.

High-temperature setup for infrared reflection spectroscopy.

We have designed an oven for optical reflection measurements at temperatures as high as 1000 K. The compact setup can be attached to any Fourier-transform infrared spectrometer using a microscope. The details of the layout, operation, and performance are discussed as well as ways for reference measurements and data correction. Finally, the high-temperature setup is utilized to determine the infrared reflectivity of tungsten up to T = 1000 K, which can serve as a reference mirror for future experiments.

Tunable sub-terahertz resonance absorption in high-coercivity magnetodielectric ceramics.

Recently, giant coercivities (20-42 kOe) and sub-terahertz natural ferromagnetic resonance (NFMR) at 100-300 GHz were observed for single-domain M-type hexaferrite particles with high aluminum substitution. Herein, we fabricated dense ceramics of Sr0.67Ca0.33Fe8Al4O19 and, for the first time, investigated their magnetostatic and magnetodynamic properties in the temperature range of 5-300 K. It was shown that dense ceramics maintain their high magnetic hardness (a coercivity of 10-20 kOe) and NFMR frequencies of 140-200 GHz durably in the entire temperature range. Magnetizing the initially non-magnetized ceramics leads to a considerable decrease in the resonance absorption and to almost complete vanishing of the resonance line at 5 kOe. At the same time, an efficient linear frequency tuning by the external magnetic field was observed for the remanent sample. These findings open new horizons for developing industrial terahertz electronics based on dielectric ferrimagnets.

Radio frequency dielectric measurements in diamond anvil cells.

We present the modifications, performance, and test of a diamond anvil cell for radio frequency dielectric spectroscopy studies of single crystals that can be used from room temperature down to 4 K and up to pressures of 5-6 GPa. Continuous frequency-dependent measurements between 5 Hz and 1 MHz can be performed with this modified pressure cell. The cell has an excellent performance with temperature-, frequency-, and pressure-independent stray capacitance of around 2 pF, enabling us to use relatively small samples with a weak dielectric response.

Far-infrared spectroscopy on free-standing protein films under defined temperature and hydration control.

The functionality of proteins is governed by their dynamics. We have performed a systematic investigation on four different proteins in the far-infrared spectral region under control of the two external parameters that have the strongest influence on the dynamics, namely temperature and hydration. The absorption measurements covering the frequency range from 40 cm(-1) to 690 cm(-1) (1-20 THz) close the gap between the well-studied mid-infrared and the recent THz investigations. By preparing the proteins as free-standing films, we achieve unprecedented reproducibility. Besides a featureless slope in the THz range, we can identify absorption peaks characteristic for each protein and others common to several proteins. We fit the spectra to extract the peak positions and suggest assignments for them. The far-infrared absorption spectra of all proteins are basically independent on hydration. By a detailed analysis of the sorption isotherms this can be explained by the low absorption of biological water, which resembles more the behavior of ice than that of liquid water.

In Vitro Comparison of Two Electromagnetic Shockwave Generators: Low-Pressure Wide Focus vs High-Pressure Small Focus- Impact on Initial Stone Fragmentation and Final Stone Comminution.

Context: Recently developed concepts for higher efficacy extracorporeal shockwave lithotripsy with low-pressure wide focus systems resulting in finer fragmentation of the calculi. Objective: To compare two different electromagnetic shockwave sources (low-pressure wide focus [Xinin Lithotripter, XL] vs high-pressure small focus [Siemens Lithoskop, SL]) by sound field measurements and in vitro fragmentation. Evidence Acquisition: The CS-2012A XX-ES lithotripter (self-focusing electromagnetic shockwave generator with concave spherical curved electrical coil; XL) was compared to the (SL) (electromagnetic generator with a flat electric coil with an acoustical lens). Different sound field measurements were performed using a fiber-optic hydrophone. Measurements at three different power settings (XL: 8.0, 9.3, and 10.3 kV and SL: Level 1, 5, and 8). Ten AST stones and 15 BegoStones (9.3 kV, Level 3) with a frequency of 90/minute (SL) and 20/minute (XL). Number of impulses to the first crack and for complete stone comminution (residual fragments <2 mm) was documented. Results: The median number of shockwaves for the first crack in AST stones with the XL was 12 (10-14) and 7 with the SL (6-9). Complete disintegration was accomplished after 815 (782-824) shockwaves with XL and 702 (688-712) with SL. The difference was not statistically significant. The median number of shockwaves to produce the first crack in BegoStones was 524 (504-542) with XL and only 151 (137-161) with SL. Numbers of shockwaves for complete disintegration did not differ significantly (XL: 2518 vs SL: 2287). Using a wide focus with low pressure shows more homogeneous disintegration. Conclusion: Two stone models showed significant differences regarding form and time of the initial fragmentation. Impulses for stone comminution did not differ significantly. The advantages of a low-pressure wide-focus system include minimal trauma and a homogeneous fragment size but is more time consuming. High-pressure small-focus systems are clinically effective.