Single-particle and collective excitations of polar water molecules confined in nano-pores within a cordierite crystal lattice.

Recently, the low-temperature phase of water molecules confined within nanocages formed by the crystalline lattice of water-containing cordierite crystals has been reported to comprise domains with ferroelectrically ordered dipoles within the a, b-planes which are antiferroelectrically alternating along the c-axis. In the present work, comprehensive broad-band dielectric spectroscopy is combined with specific heat studies and molecular dynamics and Monte Carlo simulations in order to investigate in more detail the collective modes and single-particle excitations of nanoconfined water molecules. From DFT-MD simulations we reconstruct the potential-energy landscape experienced by the H2O molecules. A rich set of anisotropic temperature-dependent excitations is observed in the terahertz frequency range. Their origin is associated with the complex rotational/translational vibrations of confined H2O molecules. A strongly temperature dependent relaxational excitation, observed at radio-microwave frequencies for the electric field parallel to the crystallographic a-axis, E||a is analyzed in detail. The temperature dependences of loss-peak frequency and dielectric strength of the excitation together with specific heat data confirm a ferroelectric order-disorder phase transition at T0 ≈ 3 K in the network of H2O dipoles. Additional dielectric data are also provided for polarization E||b, too. Overall, these combined experimental investigations enable detailed conclusions concerning the dynamics of the confined water molecules that develop within their microscopic energy landscapes.

Dielectric ordering of water molecules arranged in a dipolar lattice.

Intermolecular hydrogen bonds impede long-range (anti-)ferroelectric order of water. We confine H2O molecules in nanosized cages formed by ions of a dielectric crystal. Arranging them in channels at a distance of ~5 Å with an interchannel separation of ~10 Å prevents the formation of hydrogen networks while electric dipole-dipole interactions remain effective. Here, we present measurements of the temperature-dependent dielectric permittivity, pyrocurrent, electric polarization and specific heat that indicate an order-disorder ferroelectric phase transition at T0 ≈ 3 K in the water dipolar lattice. Ab initio molecular dynamics and classical Monte Carlo simulations reveal that at low temperatures the water molecules form ferroelectric domains in the ab-plane that order antiferroelectrically along the channel direction. This way we achieve the long-standing goal of arranging water molecules in polar order. This is not only of high relevance in various natural systems but might open an avenue towards future applications in biocompatible nanoelectronics.

Spin-Reorientation-Induced Band Gap in Fe_{3}Sn_{2}: Optical Signatures of Weyl Nodes.

Temperature- and frequency-dependent infrared spectroscopy identifies two contributions to the electronic properties of the magnetic kagome metal Fe_{3}Sn_{2}: two-dimensional Dirac fermions and strongly correlated flat bands. The interband transitions within the linearly dispersing Dirac bands appear as a two-step feature along with a very narrow Drude component due to intraband contribution. Low-lying absorption features indicate flat bands with multiple van Hove singularities. Localized charge carriers are seen as a Drude peak shifted to finite frequencies. The spectral weight is redistributed when the spins are reoriented at low temperatures; a sharp mode appears suggesting the opening of a gap due to the spin reorientation as the sign of additional Weyl nodes in the system.

Magneto-Optics of a Weyl Semimetal beyond the Conical Band Approximation: Case Study of TaP.

Landau-level spectroscopy, the optical analysis of electrons in materials subject to a strong magnetic field, is a versatile probe of the electronic band structure and has been successfully used in the identification of novel states of matter such as Dirac electrons, topological materials or Weyl semimetals. The latter arise from a complex interplay between crystal symmetry, spin-orbit interaction, and inverse ordering of electronic bands. Here, we report on unusual Landau-level transitions in the monopnictide TaP that decrease in energy with increasing magnetic field. We show that these transitions arise naturally at intermediate energies in time-reversal-invariant Weyl semimetals where the Weyl nodes are formed by a partially gapped nodal-loop in the band structure. We propose a simple theoretical model for electronic bands in these Weyl materials that captures the collected magneto-optical data to great extent.

Sub-lattice of Jahn-Teller centers in hexaferrite crystal.

A novel type of sub-lattice of the Jahn-Teller (JT) centers was arranged in Ti-doped barium hexaferrite BaFe12O19. In the un-doped crystal all iron ions, sitting in five different crystallographic positions, are Fe3+ in the high-spin configuration (S = 5/2) and have a non-degenerate ground state. We show that the electron-donor Ti substitution converts the ions to Fe2+ predominantly in tetrahedral coordination, resulting in doubly-degenerate states subject to the [Formula: see text] problem of the JT effect. The arranged JT complexes, Fe2+O4, their adiabatic potential energy, non-linear and quantum dynamics, have been studied by means of ultrasound and terahertz-infrared spectroscopies. The JT complexes are sensitive to external stress and applied magnetic field. For that reason, the properties of the doped crystal can be controlled by the amount and state of the JT complexes.

Anomalously High Proton Conduction of Interfacial Water.

Water at the solid-liquid interface exhibits an anomalous ionic conductivity and dielectric constant compared to bulk water. Both phenomena still lack a detailed understanding. Here, we report radio-frequency measurements and analyses of the electrodynamic properties of interfacial water confined in nanoporous matrices formed by diamond grains of various sizes, ranging from 5 nm to 0.5 µm in diameter. Contrary to bulk water, the charge-carrying protons/holes in interfacial water are not mutually screened, allowing for higher mobility in the external electric field. Thus, the protonic conductivity reaches a maximum value, which can be 5 orders of magnitude higher than that of bulk water. Our results aid in the understanding of physical and chemical properties of water confined in porous materials and pave the way to the development of new type of highly efficient proton-conductive materials for applications in electrochemical energy systems, membrane separations science, and nanofluidics.

Internal strain tunes electronic correlations on the nanoscale.

In conventional metals, charge carriers basically move freely. In correlated electron materials, however, the electrons may become localized because of strong Coulomb interactions, resulting in an insulating state. Despite considerable progress in the last decades, elucidating the driving mechanisms that suppress metallic charge transport, the spatial evolution of this phase transition remains poorly understood on a microscopic scale. Here, we use cryogenic scanning near-field optical microscopy to study the metal-to-insulator transition in an electronically driven charge-ordered system with a 20-nm spatial resolution. In contrast to common mean-field considerations, we observe pronounced phase segregation with a sharp boundary between metallic and insulating regions evidencing its first-order nature. Considerable strain in the crystal spatially modulates the effective electronic correlations within a few micrometers, leading to an extended "zebra" pattern of metallic and insulating stripes. We can directly monitor the spatial strain distribution via a gradual enhancement of the optical conductivity as the energy gap is depressed. Our observations shed new light on previous analyses of correlation-driven metal-insulator transitions.

Linear-in-Frequency Optical Conductivity in GdPtBi due to Transitions near the Triple Points.

The complex optical conductivity of the half-Heusler compound GdPtBi is measured in a frequency range from 20 to 22 000 cm^{-1} (2.5 meV-2.73 eV) at temperatures down to 10 K in zero magnetic field. We find the real part of the conductivity, σ_{1}(ω), to be almost perfectly linear in frequency over a broad range from 50 to 800 cm^{-1} (∼6-100 meV) for T≤50 K. This linearity strongly suggests the presence of three-dimensional linear electronic bands with band crossings (nodes) near the chemical potential. Band-structure calculations show the presence of triple points, where one doubly degenerate and one nondegenerate band cross each other in close vicinity of the chemical potential. From a comparison of our data with the optical conductivity computed from the band structure, we conclude that the observed nearly linear σ_{1}(ω) originates as a cumulative effect from all the transitions near the triple points.

Free-carrier dynamics in Au2Pb probed by optical conductivity measurements.

We measured the optical reflectivity of the Dirac material Au2Pb in a broad frequency range (30-48 000 cm-1) for temperatures between 9 and 300 K. The optical conductivity, computed from the reflectivity, is dominated by free-carrier contributions from topologically trivial bulk bands at all temperatures. The temperature-independent total plasma frequency of these carriers is [Formula: see text] eV. Overall, optical response of Au2Pb is typically metallic with no signs of localization and bad-metal behavior.

Low-Energy Excitations in Quantum Spin Liquids Identified by Optical Spectroscopy.

The electrodynamic response of organic spin liquids with highly frustrated triangular lattices has been measured in a wide energy range. While the overall optical spectra of these Mott insulators are governed by transitions between the Hubbard bands, distinct in-gap excitations can be identified at low temperatures and frequencies, which we attribute to the quantum-spin-liquid state. For the strongly correlated ß^{'}-EtMe_{3}Sb[Pd(dmit)_{2}]_{2}, we discover enhanced conductivity below 175 cm^{-1}, comparable to the energy of the magnetic coupling J≈250 K. For ω→0, these low-frequency excitations vanish faster than the charge-carrier response subject to Mott-Hubbard correlations, resulting in a dome-shaped band peaked at 100 cm^{-1}. Possible relations to spinons, magnons, and disorder are discussed.

Quantum spin liquids unveil the genuine Mott state.

The localization of charge carriers by electronic repulsion was suggested by Mott in the 1930s to explain the insulating state observed in supposedly metallic NiO. The Mott metal-insulator transition has been subject of intense investigations ever since1-3-not least for its relation to high-temperature superconductivity4. A detailed comparison to real materials, however, is lacking because the pristine Mott state is commonly obscured by antiferromagnetism and a complicated band structure. Here we study organic quantum spin liquids, prototype realizations of the single-band Hubbard model in the absence of magnetic order. Mapping the Hubbard bands by optical spectroscopy provides an absolute measure of the interaction strength and bandwidth-the crucial parameters that enter calculations. In this way, we advance beyond conventional temperature-pressure plots and quantitatively compose a generic phase diagram for all genuine Mott insulators based on the absolute strength of the electronic correlations. We also identify metallic quantum fluctuations as a precursor of the Mott insulator-metal transition, previously predicted but never observed. Our results suggest that all relevant phenomena in the phase diagram scale with the Coulomb repulsion U, which provides a direct link to unconventional superconductivity in cuprates and other strongly correlated materials.

Pressure cell for radio-frequency dielectric measurements at low temperatures.

We present the design, test, and performance of a piston type pressure cell for low-temperature dielectric measurements up to 10 kbar with particular emphasis on the electrical feedthrough for four coaxial cables and four conventional copper wires. The coaxial cables provide proper shielding of the applied test signal; a commercial continuous flow cryostat allows us to minimize the total cable length enabling temperature and pressure-dependent dielectric spectroscopy measurements down to 8 K and up to 5 MHz. We performed open compensation measurements, i.e., background measurements of the response originating from the pressure setup without a sample, to obtain its high frequency characteristics. The stray capacitance of the pressure setup is determined as Cstray = 40 fF, making it possible to measure small single crystals with a weak dielectric response. The proper operation is verified by comparing measurements of a test sample in the pressure setup at ambient pressure and in a standard dielectric spectroscopy setup.

Terahertz-infrared spectroscopy of Shewanella oneidensis MR-1 extracellular matrix.

Employing optical spectroscopy we have performed a comparative study of the dielectric response of extracellular matrix and filaments of electrogenic bacteria Shewanella oneidensis MR-1, cytochrome c, and bovine serum albumin. Combining infrared transmission measurements on thin layers with data of the terahertz spectra, we obtain the dielectric permittivity and AC conductivity spectra of the materials in a broad frequency band from a few cm-1 up to 7000 cm-1 in the temperature range from 5 to 300 K. Strong absorption bands are observed in the three materials that cover the range from 10 to 300 cm-1 and mainly determine the terahertz absorption. When cooled down to liquid helium temperatures, the bands in Shewanella oneidensis MR-1 and cytochrome c reveal a distinct fine structure. In all three materials, we identify the presence of liquid bound water in the form of librational and translational absorption bands at ≈ 200 and ≈ 600 cm-1, respectively. The sharp excitations seen above 1000 cm-1 are assigned to intramolecular vibrations.

Near-infrared optical investigations of snow, ice, and water layers on diffuse reflecting surfaces.

While most experiments on water or ice utilize rather complex, elaborate, and expensive apparatus in order to obtain reliable optical data, here we present a simple and affordable setup that enables us to perform near-infrared measurements on water, ice, and snow on top of rough diffuse reflecting surfaces such as concrete, stone, pavement, or asphalt. By using the properties of diffuse scattering instead of specular reflection, we are able to determine the imaginary part of the refraction index of water without using any liquid cells. In addition, we demonstrate that the snow spectra can be well described by newly developed two-dimensional ray tracing simulations.

Flat Optical Conductivity in ZrSiS due to Two-Dimensional Dirac Bands.

ZrSiS exhibits a frequency-independent interband conductivity σ(ω)=const(ω)≡σ_{flat} in a broad range from 250 to 2500 cm^{-1} (30-300 meV). This makes ZrSiS similar to (quasi-)two-dimensional Dirac electron systems, such as graphite and graphene. We assign the flat optical conductivity to the transitions between quasi-two-dimensional Dirac bands near the Fermi level. In contrast to graphene, σ_{flat} is not universal but related to the length of the nodal line in the reciprocal space, k_{0}. Because of spin-orbit coupling, the discussed Dirac bands in ZrSiS possess a small gap Δ, for which we determine an upper bound max(Δ)=30 meV from our optical measurements. At low temperatures the momentum-relaxation rate collapses, and the characteristic length scale of momentum relaxation is of the order of microns below 50 K.

Observation of dielectric universalities in albumin, cytochrome C and Shewanella oneidensis MR-1 extracellular matrix.

The electrodynamics of metals is well understood within the Drude conductivity model; properties of insulators and semiconductors are governed by a gap in the electronic states. But there is a great variety of disordered materials that do not fall in these categories and still respond to external field in an amazingly uniform manner. At radiofrequencies delocalized charges yield a frequency-independent conductivity σ 1(ν) whose magnitude exponentially decreases while cooling. With increasing frequency, dispersionless conductivity starts to reveal a power-law dependence σ 1(ν)∝ν s with s < 1 caused by hopping charge carriers. At low temperatures, such Universal Dielectric Response can cross over to another universal regime with nearly constant loss ε″∝σ1/ν = const. The powerful research potential based on such universalities is widely used in condensed matter physics. Here we study the broad-band (1-1012 Hz) dielectric response of Shewanella oneidensis MR-1 extracellular matrix, cytochrome C and serum albumin. Applying concepts of condensed matter physics, we identify transport mechanisms and a number of energy, time, frequency, spatial and temperature scales in these biological objects, which can provide us with deeper insight into the protein dynamics.

Vibrational states of nano-confined water molecules in beryl investigated by first-principles calculations and optical experiments.

Using quantum mechanical calculations within density functional theory, we provide a comprehensive analysis of infrared-active excitation of water molecules confined in nanocages of a beryl crystal lattice. We calculate infrared-active modes including the translational, librational, and mixed-type resonances of regular and heavy water molecules. The results are compared to the experimental spectra measured for the two principal polarizations of the electric field: parallel and perpendicular to the crystallographic c-axis. Good agreement is achieved between calculated and measured isotopic shifts of the normal modes. We analyze the vibrational modes in connection with the structural characteristics and arrangements of water molecules within the beryl crystal. Specific atomic displacements are assigned to each experimentally detected vibrational mode resolving the properties of nano-confined water on scales not accessible by experiments. Our results elucidate the applicability and efficiency of a combined experimental and computational approach for describing and an in-depth understanding of nano-confined water, and pave the way for future studies of more complex systems.

Membrane-based torque magnetometer: Enhanced sensitivity by optical readout of the membrane displacement.

The design and realization of a torque magnetometer is reported that reads the deflection of a membrane by optical interferometry. The compact instrument allows for low-temperature measurements of tiny crystals less than a microgram with a significant improvement in sensitivity, signal-to-noise ratio as well as data acquisition time compared with conventional magnetometry and offers an enormous potential for further improvements and future applications in different fields. Magnetic measurements on single-molecule magnets demonstrate the applicability of the membrane-based torque magnetometer.

Pressure dependence of the metal-insulator transition in κ-(BEDT-TTF)2Hg(SCN)2Cl: optical and transport studies.

The two-dimensional organic conductor κ-(BEDT-TTF)2-Hg(SCN)2Cl exhibits a pronounced metal-insulator transition at [Formula: see text] K. From the splitting of the molecular vibrations, the phase transition can be unambiguously assigned to charge-ordering with [Formula: see text]. We have investigated the pressure evolution of this behavior by temperature-dependent electrical transport measurements and optical investigations applying hydrostatic pressure up to 12 kbar. The data reveal a mean-field like down-shift of [Formula: see text] with a critical pressure of [Formula: see text] kbar and a metallic state above the suppression of the charge-ordered state; no traces of superconductivity could be identified down to T = 1.5 K. As the charge order [Formula: see text] sets in abruptly with decreasing temperature, its size remains unaffected by pressure. However, the fraction of charge imbalanced molecules decreases until it is completely absent above 1.6 kbar.

Incipient ferroelectricity of water molecules confined to nano-channels of beryl.

Water is characterized by large molecular electric dipole moments and strong interactions between molecules; however, hydrogen bonds screen the dipole-dipole coupling and suppress the ferroelectric order. The situation changes drastically when water is confined: in this case ordering of the molecular dipoles has been predicted, but never unambiguously detected experimentally. In the present study we place separate H2O molecules in the structural channels of a beryl single crystal so that they are located far enough to prevent hydrogen bonding, but close enough to keep the dipole-dipole interaction, resulting in incipient ferroelectricity in the water molecular subsystem. We observe a ferroelectric soft mode that causes Curie-Weiss behaviour of the static permittivity, which saturates below 10 K due to quantum fluctuations. The ferroelectricity of water molecules may play a key role in the functioning of biological systems and find applications in fuel and memory cells, light emitters and other nanoscale electronic devices.