arXiv subjects

P. Lunkenheimer

Publications and source records attributed to P. Lunkenheimer.

At least 37 records · Page 2Linked to original sources

arXiv2019

Hertz-to-terahertz dielectric response of nanoconfined water molecules

Broad-band dielectric spectroscopy, heat capacity measurements and molecular dynamic simulations are applied to study excitations of interacting electric dipoles spatially arranged in a network with an inter-dipole distance of 5-10 A. The dipoles with magnitude of 1.85 Debye are represented by single H2O molecules located in voids (0.5 nm size) formed by ions of the crystal lattice of cordierite. We discover emergence of nontrivial disordered paraelectric phase of dipolar system with signs of phase transition below 3 K.

cond-mat.mtrl-sci↗

arXiv2019

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.

cond-mat.dis-nn↗

arXiv2019

THz excitations in α-RuCl3: Majorana fermions, rigid-plane shear and compression modes

Spin liquids may host emergent quasiparticles, collective excitations of the spin degrees of freedom with characteristic features of Majorana fermions, which experimentally are detectable by broad excitation continua due to spin fractionalization. The latter is predicted for the Kitaev spin liquid, an exactly solvable model with bond-dependent interactions on a two-dimensional honeycomb lattice. Here we report on detailed THz experiments in α-RuCl3, identifying these characteristic fingerprints of Majorana fermions. The continuum intensity decreases and finally vanishes on increasing temperature. It partly overlaps with phonon modes representing characteristic sliding and compression modes of the van der Waals bonded molecular layers.

cond-mat.str-el↗

arXiv2019

Ionic conductivity of deep eutectic solvents: The role of orientational dynamics and glassy freezing

We have performed a thorough examination of the reorientational relaxation dynamics and the ionic charge transport of three typical deep eutectic solvents, ethaline, glyceline and reline by broadband dielectric spectroscopy. Our experiments cover a broad temperature range from the low-viscosity liquid down to the deeply supercooled state, allowing to investigate the significant influence of glassy freezing on the ionic charge transport in these systems. In addition, we provide evidence for a close coupling of the ionic conductivity in these materials to reorientational dipolar motions which should be considered when searching for deep eutectic solvents optimized for electrochemical applications.

cond-mat.soft↗

arXiv2019

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.

cond-mat.dis-nn↗

arXiv2018

Orbital-Order Driven Ferroelectricity and Dipolar Relaxation Dynamics in Multiferroic GaMo$_4$S$_8$

We present the results of broadband dielectric spectroscopy of GaMo$_4$S$_8$, a lacunar spinel system that recently was shown to exhibit non-canonical, orbitally-driven ferroelectricity. Our study reveals complex relaxation dynamics of this multiferroic material, both above and below its Jahn-Teller transition at T$_{\textrm{JT}}=47$ K. Above T$_{\textrm{JT}}$, two types of coupled dipolar-orbital dynamics seem to compete: relaxations within cluster-like regions with short-range polar order like in relaxor ferroelectrics and critical fluctuations of only weakly interacting dipoles, the latter resembling the typical dynamics of order-disorder type ferroelectrics. Below the Jahn-Teller transition, the onset of orbital order drives the system into long-range ferroelectric order and dipolar dynamics within the ferroelectric domains is observed. The coupled dipolar and orbital relaxation behavior of GaMo$_4$S$_8$ above the Jahn-Teller transition markedly differs from that of the skyrmion host GaV$_4$S$_8$, which seems to be linked to differences in the structural distortions of the two systems on the unit-cell level.

cond-mat.str-el↗

arXiv2018

Importance of reorientational dynamics for the charge transport in ionic liquids

Most ionic liquids contain at least one rather complex ion species exhibiting a dipolar moment. In the present work, we provide a thorough evaluation of broadband dielectric spectra of 12 ionic liquids taking into account the often neglected reorientational dynamics of these ions. We confirm that this dynamics leads to a clear relaxational signature in the spectra, a fact that so far only was considered in few previous works. The obtained reorientational relaxation times are well consistent with earlier inelastic light-scattering and high-frequency dielectric investigations. Evaluating our dielectric spectra in terms of reorientational motions reveals a close coupling of the ion-rotation dynamics to the ionic charge transport in a broad temperature range from the low-viscosity liquid above room temperature deep into the high-viscosity supercooled state close to Tg. This coupling does not seem to be mediated by the viscosity but probably is of more direct nature, pointing to a revolving-door mechanism as also considered for plastic-crystalline ionic conductors. Our results show that the reorientational motion of the dipolar ions plays a significant and so far widely overlooked role for the ionic charge transport in ionic liquids.

cond-mat.soft↗

arXiv2018

Third and Fifth Harmonic Responses in Viscous Liquids

We review the works devoted to third and fifth harmonic susceptibilities in glasses, namely $χ$ (3) 3 and $χ$ (5) 5. We explain why these nonlinear responses are especially well adapted to test whether or not some amorphous correlations develop upon cooling. We show that the experimental frequency and temperature dependences of $χ$ (3) 3 and of $χ$ (5) 5 have anomalous features, since their behavior is qualitatively different to that of an ideal gas, which is the high-temperature limit of a fluid. Most of the works have interpreted this anomalous behavior as reflecting the growth, upon cooling, of amorphously ordered domains, as predicted by the general framework of Bouchaud and Biroli (BB). We explain why most-if not all-of the challenging interpretations can be recast in a way which is consistent with that of Bouchaud and Biroli. Finally, the comparison of the anomalous features of $χ$ (5) 5 and of $χ$ (3) 3 shows that the amorphously ordered domains are compact, i.e., the fractal dimension d f is close to the dimension d of space. This suggests that the glass transition of molecular liquids corresponds to a new universality class of critical phenomena.

cond-mat.soft↗

arXiv2018

Relaxation dynamics in the one-dimensional organic charge-transfer salt δ-(EDT-TTF-CONMe$_2$)$_2$Br

A detailed investigation of the charge-ordered charge-transfer salt δ-(EDT-TTF-CONMe$_{2}$)$_{2}$Br by thermal-expansion measurements and dielectric spectroscopy reveals three dynamic processes of relaxational character. The slowest one exhibits the characteristics of glassy freezing and is ascribed to the conformational dynamics of terminal ethylene groups of the organic molecules. Such a process was previously found for related charge-transfer salts where, however, the anions form polymerlike chains, in contrast to the spherical anions of the present material. Dielectric spectroscopy reveals two additional relaxational processes. The characteristics of the faster one are consistent with excitations of a one-dimensional Wigner lattice as recently observed in this material by infrared spectroscopy, which are also accompanied by conformational changes of the molecules. However, at low temperature the ethylene-group relaxation exhibits the cooperativity-induced dramatic slowing down that is typical for glassy freezing, while the defect-related Wigner-lattice excitation follows thermally activated behavior as expected for single-dipole relaxations.

cond-mat.str-el↗

arXiv2018

Fast dynamics in glass-forming salol investigated by dielectric spectroscopy

We analyze dielectric-loss spectra of glass forming salol extending up to 400 GHz allowing for the detection of the high-frequency minimum, where the fast critical dynamics predicted by the mode-coupling theory of the glass transition should prevail. Indeed, we find such a minimum which, moreover, well fulfills the critical scaling predicted by the theory. This includes the spectral shape of the minimum, the critical temperature dependence of the minimum frequency and amplitude, and the critical temperature dependence of the alpha-relaxation rate at high temperatures. The minimum exponents a and b leading to a system parameter lambda = 0.63 and the critical temperature Tc = 256 K are all in reasonable agreement with previous investigations of salol using different methods. Salol was one of the first materials where mode-coupling theory was tested and initial dielectric measurements were taken as an argument against the universal applicability of this theory.

cond-mat.soft↗

arXiv2017

Electromagnetic-radiation absorption of water

Why does a microwave oven work? How does biological tissue absorb electromagnetic radiation? Astonishingly, we do not have a definite answer to these simple questions because the microscopic processes governing the absorption of electromagnetic waves by water are largely unclarified. This absorption can be quantified by dielectric loss spectra, which reveal a huge peak at a frequency of the exciting electric field of about 20 GHz and a gradual tailing off towards higher frequencies. The microscopic interpretation of such spectra is highly controversial and various superpositions of relaxation and resonance processes ascribed to single-molecule or molecule-cluster motions have been proposed for their analysis. By combining dielectric, microwave, THz, and far-infrared spectroscopy, here we provide nearly continuous temperature-dependent broadband spectra of water. Moreover, we find that corresponding spectra for aqueous solutions reveal the same features as pure water. However, in contrast to the latter, crystallization in these solutions can be avoided by supercooling. As different spectral contributions tend to disentangle at low temperatures, this enables to deconvolute them when approaching the glass transition under cooling. We find that the overall spectral development, including the 20 GHz feature (employed for microwave heating), closely resembles the behavior known for common supercooled liquids. Thus, water's absorption of electromagnetic waves at room temperature is not unusual but very similar to that of glass-forming liquids at elevated temperatures, deep in the low-viscosity liquid regime, and should be interpreted along similar lines.

cond-mat.soft↗

arXiv2017

Johari-Goldstein relaxation far below Tg: Experimental evidence for the Gardner transition in structural glasses?

Experimental evidence for the Gardner transition, theoretically predicted to arise deep in the glassy state of matter, is scarce. At this transition, the energy landscape sensed by the particles forming the glass is expected to become more complex. In the present work, we report the dielectric response of two typical glass formers with well-pronounced Johari-Goldstein beta relaxation following this response down to unprecedented low temperatures, far below the glass transition. As the Johari-Goldstein process is believed to arise from the local structure of the energy landscape, its investigation seems an ideal tool to seek evidence for the Gardner transition. Indeed, we find an unusual broadening of the beta relaxation below TG ~ 110 K for sorbitol and TG ~ 100 K for xylitol, in excess of the expected broadening arising from a distribution of energy barriers. Thus, these results provide hints at the presence of the Gardner transition in canonical structural glass formers.

cond-mat.soft↗

arXiv2017

Unifying different interpretations of the nonlinear response in glass-forming liquids

This work aims at reconsidering several interpretations coexisting in the recent literature concerning non-linear susceptibilities in supercooled liquids. We present experimental results on glycerol and propylene carbonate showing that the three independent cubic susceptibilities have very similar frequency and temperature dependences, both for their amplitudes and phases. This strongly suggests a unique physical mechanism responsible for the growth of these non-linear susceptibilities. We show that the framework proposed by two of us [BB, Phys. Rev. B 72, 064204 (2005)], where the growth of non-linear susceptibilities is intimately related to the growth of "glassy domains", accounts for all the salient experimental features. We then review several complementary and/or alternative models, and show that the notion of cooperatively rearranging glassy domains is a key (implicit or explicit) ingredient to all of them. This paves the way for future experiments which should deepen our understanding of glasses.

cond-mat.dis-nn↗

arXiv2017

Polar and magnetic order in GaV4Se8

In the present work, we provide results from specific heat, magnetic susceptibility, dielectric constant, ac conductivity, and electrical polarization measurements performed on the lacunar spinel GaV4Se8. With decreasing temperature, we observe a transition from the paraelectric and paramagnetic cubic state into a polar, probably ferroelectric state at 42 K followed by magnetic ordering at 18 K. The polar transition is likely driven by the Jahn-Teller effect due to the degeneracy of the V4 cluster orbitals. The excess polarization arising in the magnetic phase indicates considerable magnetoelectric coupling. Overall, the behavior of GaV4Se8 in many respects is similar to that of the skyrmion host GaV4S8, exhibiting a complex interplay of orbital, spin, lattice, and polar degrees of freedom. However, its dielectric behavior at the polar transition markedly differs from that of the Jahn-Teller driven ferroelectric GeV4S8, which can be ascribed to the dissimilar electronic structure of the Ge compound.

cond-mat.str-el↗

arXiv2017

Variation of ionic conductivity in a plastic-crystalline mixture

Ionically-conducting plastic crystals are possible candidates for solid-state electrolytes in energy-storage devices. Interestingly, the admixture of larger molecules to the most prominent molecular PC electrolyte, succinonitrile, was shown to drastically enhance its ionic conductivity. Therefore, binary mixtures seem to be a promising way to tune the conductivity of such solid-state electrolytes. However, to elucidate the general mechanisms of ionic charge transport in plastic crystals and the influence of mixing, a much broader data base is needed. In the present work, we investigate mixtures of two well-known plastic-crystalline systems, cyclohexanol and cyclooctanol, to which 1 mol% of Li ions were added. Applying differential scanning calorimetry and dielectric spectroscopy, we present a thorough investigation of the phase behavior and the ionic and dipolar dynamics of this system. All mixtures reveal plastic-crystalline phases with corresponding orientational glass-transitions. Moreover, their conductivity seems to be dominated by the "revolving-door" mechanism, implying a close coupling between the ionic translational and the molecular reorientational dynamics of the surrounding plastic-crystalline matrix. In contrast to succinonitrile-based mixtures, there is no strong variation of this coupling with the mixing ratio.

cond-mat.soft↗

arXiv2017

Optical conductivity in multiferroic GaV$_4$S$_8$ and GeV$_4$S$_8$: Phonons and electronic transitions

We report on optical spectroscopy on the lacunar spinels GaV$_4$S$_8$ and GeV$_4$S$_8$ in the spectral range from 100 to 23000 cm$^{-1}$ and for temperatures from 5 to 300 K. These multiferroic spinel systems reveal Jahn-Teller driven ferroelectricity and complex magnetic order at low temperatures. We study the infrared-active phonon modes and the low-lying electronic excitations in the cubic high-temperature phase, as well as in the orbitally and in the magnetically ordered low-temperature phases. We compare the phonon modes in these two compounds, which undergo different symmetry-lowering Jahn-Teller transitions into ferroelectric and orbitally ordered phases, and exhibit different magnetic ground states. We follow the splitting of the phonon modes at the structural phase transition and detect additional splittings at the onset of antiferromagnetic order in GeV$_4$S$_8$. We observe electronic transitions within the $d$-derived bands of the V$_4$ clusters and document a significant influence of the structural and magnetic phase transitions on the narrow electronic band gaps.

cond-mat.str-el↗

arXiv2017

Excitations and relaxation dynamics in multiferroic GeV4S8 studied by THz and dielectric spectroscopy

We report on THz time-domain spectroscopy on multiferroic GeV4S8, which undergoes orbital ordering at a Jahn-Teller transition at 30.5 K and exhibits antiferromagnetic order below 14.6 K. The THz experiments are complemented by dielectric experiments at audio and radio frequencies. We identify a low-lying excitation close to 15 cm-1, which is only weakly temperature dependent and probably corresponds to a molecular excitation within the electronic level scheme of the V4 clusters. In addition, we detect complex temperature-dependent behavior of a low-lying phononic excitation, closely linked to the onset of orbitally-driven ferroelectricity. In the high-temperature cubic phase, which is paramagnetic and orbitally disordered, this excitation is of relaxational character, becomes an overdamped Lorentzian mode in the orbitally ordered phase below the Jahn-Teller transition, and finally appears as well-defined phonon excitation in the antiferromagnetic state. Abrupt changes in real and imaginary parts of the complex dielectric permittivity show that orbital ordering appears via a structural phase transition with strong first-order character and that the onset of antiferromagnetic order is accompanied by significant structural changes, which are of first-order character, too. Dielectric spectroscopy documents that, at low frequencies, significant dipolar relaxations are present in the orbitally ordered, paramagnetic phase only. In contrast to the closely related GaV4S8, this relaxation dynamics that most likely mirrors coupled orbital and polar fluctuations does not seem to be related to the dynamic processes detected in the THz regime.

cond-mat.str-el↗

arXiv2017

Investigation of nonlinear effects in glassy matter using dielectric methods

We summarize current developments in the investigation of glassy matter using nonlinear dielectric spectroscopy. This work also provides a brief introduction into the phenomenology of the linear dielectric response of glass-forming materials and discusses the main mechanisms that can give rise to nonlinear dielectric response in this material class. Here we mainly concentrate on measurements of the conventional dielectric permittivity at high fields and the higher-order susceptibilities characterizing the 3-omega and 5-omega components of the dielectric response as performed in our group. Typical results on canonical glass-forming liquids and orientationally disordered plastic crystals are discussed, also treating the special case of supercooled monohydroxy alcohols.

cond-mat.dis-nn↗