Ions in glass forming glycerol: Close correlation of alpha and fast beta relaxation

We provide broadband dielectric loss spectra of glass-forming glycerol with varying additions of LiCl. The measurements covering frequencies up to 10 THz extend well into the region of the fast beta process, commonly ascribed to caged molecule dynamics. Aside of the known variation of the structural alpha relaxation time and a modification of the excess wing with ion content, we also find a clear influence on the shallow loss minimum arising from the fast beta relaxation. Within the framework of mode-coupling theory, the detected significant broadening of this minimum is in reasonable accord with the found variation of the alpha-relaxation dynamics. A correlation between alpha-relaxation rate and minimum position holds for all ion concentrations and temperatures, even below the critical temperature defined by mode-coupling theory.Comment: 5 pages, 5 figure

Nonlinear dielectric response of Debye, alpha, and beta relaxation in 1-propanol

We present nonlinear dielectric measurements of glass-forming 1-propanol, a prototypical example for the monohydroxy alcohols that are known to exhibit unusual relaxation dynamics, namely an additional Debye relaxation, slower than the structural alpha relaxation. Applying high ac fields of 468 kV/cm allows for a detailed investigation of the nonlinear properties of all three relaxation processes occurring in 1-propanol, namely the Debye, alpha, and beta relaxation. Both the field-induced variations of dielectric constant and loss are reported. Polarization saturation and the absorption of field energy govern the findings in the Debye-relaxation regime, well consistent with the suggested cluster-like nature of the relaxing entities. The behavior of the alpha relaxation is in good accord with the expectations for a heterogeneous relaxation scenario. Finally, the Johari-Goldstein beta-relaxation in 1-propanol seems to exhibit no or only weak field dependence, in agreement with recent findings for the excess wing of canonical glass formers.Comment: 8 pages, 4 figure

Cooperativity and Heterogeneity in Plastic Crystals Studied by Nonlinear Dielectric Spectroscopy

The glassy dynamics of plastic-crystalline cyclo-octanol and ortho-carborane, where only the molecular reorientational degrees of freedom freeze without long-range order, is investigated by nonlinear dielectric spectroscopy. Marked differences to canonical glass formers show up: While molecular cooperativity governs the glassy freezing, it leads to a much weaker slowing down of molecular dynamics than in supercooled liquids. Moreover, the observed nonlinear effects cannot be explained with the same heterogeneity scenario recently applied to canonical glass formers. This supports ideas that molecular relaxation in plastic crystals may be intrinsically non-exponential. Finally, no nonlinear effects were detected for the secondary processes in cyclo-octanol.Comment: Final version as accepted for publication in Phys. Rev. Lett. 6 pages, 5 figures (including 1 page and figure in Supplemental Material

Relaxation dynamics of a protein solution investigated by dielectric spectroscopy

In the present work, we provide a dielectric study on two differently concentrated aqueous lysozyme solutions in the frequency range from 1 MHz to 40 GHz and for temperatures from 275 to 330 K. We analyze the three dispersion regions, commonly found in protein solutions, usually termed beta-, gamma-, and delta-relaxation. The beta-relaxation, occurring in the frequency range around 10 MHz and the gamma-relaxation around 20 GHz (at room temperature) can be attributed to the rotation of the polar protein molecules in their aqueous medium and the reorientational motion of the free water molecules, respectively. The nature of the delta-relaxation, which often is ascribed to the motion of bound water molecules, is not yet fully understood. Here we provide data on the temperature dependence of the relaxation times and relaxation strengths of all three detected processes and on the dc conductivity arising from ionic charge transport. The temperature dependences of the beta- and gamma-relaxations are closely correlated. We found a significant temperature dependence of the dipole moment of the protein, indicating conformational changes. Moreover we find a breakdown of the Debye-Stokes-Einstein relation in this protein solution, i.e., the dc conductivity is not completely governed by the mobility of the solvent molecules. Instead it seems that the dc conductivity is closely connected to the hydration shell dynamics.Comment: 11 pages, 7 figure

Crystal structure, incommensurate magnetic order and ferroelectricity in mn1−x_{1-x}cux_{x}wo4{_4} (x=0-0.19)

We have carried out a systematic study on the effect of Cu doping on nuclear, magnetic, and dielectric properties in Mn$_{1-x}$Cu$_{x}$WO$_4$ for ${0}\leq{x}\leq{0.19}$ by a synergic use of different techniques, viz, heat capacity, magnetization, dielectric, and neutron powder diffraction measurements. Via heat capacity and magnetization measurements we show that with increasing Cu concentration magnetic frustration decreases, which leads to the stabilization of commensurate magnetic ordering. This was further verified by temperature-dependent unit cell volume changes derived from neutron diffraction measurements which was modeled by the Gr\"{u}neisen approximation. Dielectric measurements show a low temperature phase transition below about 9-10 K. Further more, magnetic refinements reveal no changes below this transition indicating a possible spin-flop transition which is unique to the Cu doped system. From these combined studies we have constructed a magnetoelectric phase diagram of this compound.Comment: 9 pages, 9 figures, accepted for publication in PR

Tuning orbital-selective correlation effects in superconducting Rb0.75_{0.75}Fe1.6_{1.6}Se2−z_{2-z}Sz_z

We report on terahertz time-domain spectroscopy on superconducting and metallic iron chalcogenides Rb$_{0.75}$Fe$_{1.6}$Se$_{2-z}$S$_z$. The superconducting transition is reduced from $T_c=$ 32 K ($z=0$) to 22 K ($z=1.0$), and finally suppressed ($z=1.4$) by isoelectronic substitution of Se with S. Dielectric constant and optical conductivity exhibit a metal-to-insulator transition associated with an orbital-selective Mott phase. This orbital-selective Mott transition appears at higher temperature $T_{met}$ with increasing sulfur content, identifying sulfur substitution as an efficient parameter to tune orbital-dependent correlation effects in iron-chalcogenide superconductors. The reduced correlations of the $d_{xy}$ charge carriers can account for the suppression of the superconductivity and the pseudogap-like feature between $T_c$ and $T_{met}$ that was observed for $z=0$.Comment: 6 pages, 4 figure

Heat capacity of the quantum magnet TiOCl

Measurements of the heat capacity C(T,H) of the one-dimensional quantum magnet TiOCl are presented for temperatures 2K < T < 300K and magnetic fields up to 5T. Distinct anomalies at 91K and 67K signal two subsequent phase transitions. The lower of these transitions clearly is of first order and seems to be related to the spin degrees of freedom. The transition at 92K probably involves the lattice and/or orbital moments. A detailed analysis of the data reveals that the entropy change through both transitions is surprisingly small (~ 0.1R), pointing to the existence strong fluctuations well into the non-ordered high-temperature phase. No significant magnetic field dependence was detected.Comment: 4 pages, 2 figure