Ionic conductivity and relaxation dynamics in plastic-crystals with nearly globular molecules

We have performed a dielectric investigation of the ionic charge transport and the relaxation dynamics in plastic-crystalline 1-cyano-adamantane (CNA) and in two mixtures of CNA with the related plastic crystals adamantane or 2-adamantanon. Ionic charge carriers were provided by adding 1% of Li salt. The molecules of these compounds have nearly globular shape and, thus, the so-called revolving-door mechanism assumed to promote ionic charge transport via molecular reorientations in other PC electrolytes, should not be active here. Indeed, a comparison of the dc resistivity and the reorientational alpha-relaxation times in the investigated PCs, reveals complete decoupling of both dynamics. Similar to other PCs, we find a significant mixing-induced enhancement of the ionic conductivity. Finally, these solid-state electrolytes reveal a second relaxation process, slower than the alpha-relaxation, which is related to ionic hopping. Due to the mentioned decoupling, it can be unequivocally detected and is not superimposed by the reorientational contributions as found for most other ionic conductors.Comment: 9 pages, 7 figure

Ferroelectric properties of charge-ordered alpha-(BEDT-TTF)2I3

A detailed investigation of the out-of-plane electrical properties of charge-ordered alpha-(BEDT-TTF)2I3 provides clear evidence for ferroelectricity. Similar to multiferroic alpha-(BEDT-TTF)2Cu[N(CN)2]Cl, the polar order in this material is ascribed to the occurrence of bond- and site-centered charge order. Dielectric response typical for relaxor ferroelectricity is found deep in the charge-ordered state. We suggest an explanation in terms of the existence of polar and nonpolar stacks of the organic molecules in this material, preventing long-range ferroelectricity. The results are discussed in relation to the formation or absence of electronic polar order in related charge-transfer salts.Comment: 8 pages, 4 figures. Revised version as accepted for publication in Phys. Rev.

Thermodynamic evidence of fractionalized excitations in {\alpha}-RuCl3

Fractionalized excitations are of considerable interest in recent condensed-matter physics. Fractionalization of the spin degrees of freedom into localized and itinerant Majorana fermions are predicted for the Kitaev spin liquid, an exactly solvable model with bond-dependent interactions on a two-dimensional honeycomb lattice. As function of temperature, theory predicts a characteristic two-peak structure of the heat capacity as fingerprint of these excitations. Here we report on detailed heat-capacity experiments as function of temperature and magnetic field in high-quality single crystals of {\alpha}-RuCl3 and undertook considerable efforts to determine the exact phonon background. We measured single-crystalline RhCl3 as non-magnetic reference and performed ab-initio calculations of the phonon density of states for both compounds. These ab-initio calculations document that the intrinsic phonon contribution to the heat capacity cannot be obtained by a simple rescaling of the nonmagnetic reference using differences in the atomic masses. Sizable renormalization is required even for non-magnetic RhCl3 with its minute difference from the title compound. In {\alpha}-RuCl3 in zero magnetic field, excess heat capacity exists at temperatures well above the onset of magnetic order. In external magnetic fields far beyond quantum criticality, when long-range magnetic order is fully suppressed, the excess heat capacity exhibits the characteristic two-peak structure. In zero field, the lower peak just appears at temperatures around the onset of magnetic order and seems to be connected with canonical spin degrees of freedom. At higher fields, beyond the critical field, this peak is shifted to 10 K. The high-temperature peak located around 50 K is hardly influenced by external magnetic fields, carries the predicted amount of entropy, R/2 ln2, and may resemble remnants of Kitaev physics

Dynamical Dzyaloshinsky-Moriya interaction in KCuF3: Raman evidence for an antiferrodistortive lattice instability

In the orbitally ordered, quasi-one dimensional Heisenberg antiferromagnet KCuF3 the low-energy Eg and B1g phonon modes show an anomalous softening (25% and 13%) between room temperature and the characteristic temperature T_S = 50 K. In this temperature range a freezing-in of F ion dynamic displacements is proposed to occur. In addition, the Eg mode at about 260 cm-1 clearly splits below T_S. The width of the phonon lines above T_S follows an activated behavior with an activation energy of about 50 K. Our observations clearly evidence a reduction of the structural symmetry below T_S and indicate a strong coupling of lattice and spin fluctuations for T>T_S.Comment: 7 pages, 9 figure

Phonon anomalies and charge dynamics in Fe_{1-x}Cu_{x}Cr_{2}S_{4} single crystals

A detailed investigation of phonon excitations and charge carrier dynamics in single crystals of Fe_{1-x}Cu_{x}Cr_{2}S_{4} (x = 0, 0.2, 0.4, 0.5) has been performed by using infrared spectroscopy. In FeCr_{2}S_{4} the phonon eigenmodes are strongly affected by the onset of magnetic order. Despite enhanced screening effects, a continuous evolution of the phonon excitations can be observed in the doped compounds with x = 0.2 (metallic) and x = 0.4, 0.5 (bad metals), but the effect of magnetic ordering on the phonons is strongly reduced compared to x = 0. The Drude-like charge-carrier contribution to the optical conductivity in the doped samples indicates that the colossal magneto-resistance effect results from the suppression of spin-disorder scattering.Comment: 8 pages, 6 figure

Plastic-crystalline solid-state electrolytes: Ionic conductivity and orientational dynamics in nitrile mixtures

Many plastic crystals, molecular solids with long-range, center-of-mass crystalline order but dynamic disorder of the molecular orientations, are known to exhibit exceptionally high ionic conductivity. This makes them promising candidates for applications as solid-state electrolytes, e.g., in batteries. Interestingly, it was found that the mixing of two different plastic-crystalline materials can considerably enhance the ionic dc conductivity, an important benchmark quantity for electrochemical applications. An example is the admixture of different nitriles to succinonitrile, the latter being one of the most prominent plastic-crystalline ionic conductors. However, until now only few such mixtures were studied. In the present work, we investigate succinonitrile mixed with malononitrile, adiponitrile, and pimelonitrile, to which 1 mol% of Li ions were added. Using differential scanning calorimetry and dielectric spectroscopy, we examine the phase behavior and the dipolar and ionic dynamics of these systems. We especially address the mixing-induced enhancement of the ionic conductivity and the coupling of the translational ionic mobility to the molecular reorientational dynamics, probably arising via a "revolving-door" mechanism.Comment: 9 pages, 7 figures; revised version as accepted for publication in J. Chem. Phy

Diluted Random Fields in Mixed Cyanide Crystals

A percolation argument and a dilute compressible random field Ising model are used to present a simple model for mixed cyanide crystals. The model reproduces quantitatively several features of the phase diagrams altough some crude approximations are made. In particular critical thresholds x_c at which ferroelastic first order transitions disappear, are calculated. Moreover, transitions are found to remain first order down to x_c for all mixtures except for bromine, for which the transition becomes continuous. All the results are in full agreement with experimental data.Comment: 8 pages, late

Glycerol confined in zeolitic imidazolate frameworks: The temperature-dependent cooperativity length scale of glassy freezing

In the present work, we employ broadband dielectric spectroscopy to study the molecular dynamics of the prototypical glass former glycerol confined in two microporous zeolitic imidazolate frameworks (ZIF-8 and ZIF-11) with well-defined pore diameters of 1.16 and 1.46 nm, respectively. The spectra reveal information on the modified alpha relaxation of the confined supercooled liquid, whose temperature dependence exhibits clear deviations from the typical super-Arrhenius temperature dependence of the bulk material, depending on temperature and pore size. This allows assigning well-defined cooperativity length scales of molecular motion to certain temperatures above the glass transition. We relate these and previous results on glycerol confined in other host systems to the temperature-dependent length scale deduced from nonlinear dielectric measurements. The combined experimental data can be consistently described by a critical divergence of this correlation length as expected within theoretical approaches assuming that the glass transition is due to an underlying phase transition.Comment: 14 pages, 5 figures + Supplemental Material (4 pages, 6 figures). Final version as accepted for publicatio

31P NMR study of Na2CuP2O7: a S=1/2 two-dimensional Heisenberg antiferromagnetic system

The magnetic properties of Na2CuP2O7 were investigated by means of 31P nuclear magnetic resonance (NMR), magnetic susceptibility, and heat capacity measurements. We report the 31P NMR shift, the spin-lattice 1/T1, and spin-spin 1/T2 relaxation-rate data as a function of temperature T. The temperature dependence of the NMR shift K(T) is well described by the S=1/2 square lattice Heisenberg antiferromagnetic (HAF) model with an intraplanar exchange of J/k_B \simeq 18\pm2 K and a hyperfine coupling A = (3533\pm185) Oe/mu_B. The 31P NMR spectrum was found to broaden abruptly below T \sim 10 K signifying some kind of transition. However, no anomaly was noticed in the bulk susceptibility data down to 1.8 K. The heat capacity appears to have a weak maximum around 10 K. With decrease in temperatures, the spin-lattice relaxation rate 1/T1 decreases monotonically and appears to agree well with the high temperature series expansion expression for a S = 1/2 2D square lattice.Comment: 12 pages, 8 figures, submitted to J. Phys.: Cond. Ma