arXiv subjects

Bernhard Frick

Publications and source records attributed to Bernhard Frick.

17 recordsLinked to original sources

arXiv2021

Dynamics of Water Confined in Mesopores with Variable Surface Interaction

We have investigated the dynamics of liquid water confined in mesostructured porous silica (MCM-41) and periodic mesoporous organosilicas (PMOs) by incoherent quasielastic neutron scattering experiments. The effect of tuning the water/surface interaction from hydrophilic to more hydrophobic on the water mobility, while keeping the pore size in the range 3.5-4.1 nm, was assessed from the comparative study of three PMOs comprising different organic bridging units and the purely siliceous MCM-41 case. An extended dynamical range was achieved by combining time-of-flight (IN5B) and backscattering (IN16B) quasielastic neutron spectrometers providing complementary energy resolutions. Liquid water was studied at regularly spaced temperatures ranging from 300 K to 243 K. In all systems, the molecular dynamics could be described consistently by the combination of two independent motions resulting from fast local motion around the average molecule position and the confined translational jump diffusion of its center of mass. All the molecules performed local relaxations, whereas the translational motion of a fraction of molecules was frozen on the experimental timescale. This study provides a comprehensive microscopic view on the dynamics of liquid water confined in mesopores, with distinct surface chemistries, in terms of non-mobile/mobile fraction, self-diffusion coefficient, residence time, confining radius, local relaxation time, and their temperature dependence. Importantly, it demonstrates that the strength of the water/surface interaction determines the long-time tail of the dynamics, which we attributed to the translational diffusion of interfacial molecules, while the water dynamics in the pore center is barely affected by the interface hydrophilicity.

physics.chem-ph↗

arXiv2020

Ionic liquid dynamics in nanoporous carbon: A pore-size- and temperature-dependent neutron spectroscopy study on supercapacitor materials

The influence of spatial confinement on the thermally excited stochastic cation dynamics of the room-temperature ionic liquid 1-N-butylpyridinium bis-((trifluoromethyl)sulfonyl)imide ([BuPy][Tf_2N]) inside porous carbide-derived carbons with various pore sizes in the sub- to a few nanometer range are investigated by quasi-elastic neutron spectroscopy. Using the potential of fixed window scans, i.e. scanning a sample parameter, while observing solely one specific energy transfer value, an overview of the dynamic landscape within a wide temperature range is obtained. It is shown that already these data provide a quite comprehensive understanding of the confinement-induced alteration of the molecular mobility in comparison to the bulk. A complementary, more detailed analysis of full energy transfer spectra at selected temperatures reveals two translational diffusive processes on different time scales. Both are considerably slower than in the bulk liquid and show a decrease of the respective self-diffusion coefficients with decreasing nanopore size. Different thermal activation energies for molecular self-diffusion in nanoporous carbons with similar pore size indicate the importance of pore morphology on the molecular mobility, beyond the pure degree of confinement. In spite of the dynamic slowing down we can show that the temperature range of the liquid state upon nanoconfinement is remarkably extended to much lower temperatures, which is beneficial for potential technical applications of such systems.

physics.chem-ph↗

arXiv2019

Mapping Microstructural Dynamics up to the Nanosecond of the Conjugated Polymer P3HT in the Solid State

We present a detailed study of the structure-dynamics relationship of regio-regular and regio-random PEHT using different neutron scattering techniques. Deuteration is employed to modulate the coherent and incoherent cross-sections, allowing particularly to access both self-motions and collective dynamics of the materials. The measurements are underpinned by extensive quantitative calculations using classical MD, as well as first principles quantum chemistry. MD reproduced well the main structural features and slow motions, and shed light on differences in collective dynamics between Q-values linked with the $π-π$ stacking and the lamellar stacking, with the crystalline phase being the most impacted. On the other hand MD led to a limited description of molecular vibrations. In this context, first principles molecular calculations described well the high-energy vibrational features ( $>$ 900 cm$^{-1}$ ), while periodic calculations allowed to better describe the low- and mid-energy vibrational ranges ( 200-900 cm$^{-1}$ ). The mid-energy range is predominantly associated with both intra-molecular and inter-molecular mode coupling, which encloses information about both the polymer conformation and the polymer packing at short range. One of the outcomes of this study is the validation of the common assumption made that RRa-P3HT is a good approximation for the amorphous phase of RR-P3HT at the macroscopic level. The present work helps to clarify unambiguously the latter point which has been largely overlooked in the literature. We highlight the importance to complement optical spectroscopy techniques with inelastic neutron scattering. The latter offering the advantage of being insensitive to the delocalized $π$-electron system, and thus enabling to infer relevant quantities like conjugation lengths, for instance, impacting properties of conjugated polymer.

cond-mat.mtrl-sci↗

arXiv2018

Isochronal superposition and density scaling of the $α$-relaxation from pico- to millisecond

The relaxation dynamics in two van der Waals bonded and one hydrogen-bonding molecular liquids is studied as a function of pressure and temperature by incoherent neutron scattering using simultaneous dielectric spectroscopy. The dynamics is studied in a range of alpha relaxation times from nano- to milliseconds, primarily in the equilibrium liquid state. In this range we find that isochronal superposition and density scaling work not only for the two van der Waals liquids, but also for the hydrogen-bonding liquid, though the density scaling exponent is much smaller for the latter. Density scaling and isochronal superposition are seen to break down for intra-molecular dynamics when it is separated in time from the $α$-relaxation in close agreement with previous observations from molecular dynamics simulations.

cond-mat.soft↗

arXiv2017

High-pressure cell for simultaneous dielectric and neutron spectroscopy

In this article we report on the design, manufacture and testing of a high-pressure cell for doing simultaneous dielectric and neutron spectroscopy. This cell is a unique tool for studying dynamics on different timescales, from kilo- to picoseconds, covering universal features such as the alpha relaxation and fast vibrations at the same time. The cell, constructed in cylindrical geometry, is made in high-strength aluminum alloy and operates up to 500 MPa in a temperature range between roughly 2 and 320 K. In order to measure the scattered neutron intensity and the sample capacitance simultaneously, a cylindrical capacitor is positioned within the bore of the high-pressure container. The capacitor consists of two concentric electrodes separated by insulating spacers. The performance of this setup has been successfully verified by collecting simultaneous dielectric and neutron spectroscopy data on dipropylene glycol, using both backscattering and time-of-flight instruments. We have carried out the experiments at different combinations of temperature and pressure in both supercooled liquid and glassy state.

physics.ins-det↗

arXiv2017

Evidence of a one-dimensional thermodynamic phase diagram for simple glass-formers

The glass transition plays a central role in nature as well as in industry, ranging from biological systems such as proteins and DNA to polymers and metals. Yet the fundamental understanding of the glass transition which is a prerequisite for optimized application of glass formers is still lacking. Glass formers show motional processes over an extremely broad range of timescales, covering more than ten orders of magnitude, meaning that a full understanding of the glass transition needs to comprise this tremendous range in timescales. Here we report on first-time simultaneous neutron and dielectric spectroscopy investigations of three glass-forming liquids, probing in a single experiment the full range of dynamics. For two van der Waals liquids we locate in the pressure-temperature phase diagram lines of identical dynamics of the molecules on both second and picosecond timescales. This confirms predictions of the isomorph theory and effectively reduces the phase diagram from two to one dimension. The implication is that dynamics on widely different timescales are governed by the same underlying mechanisms.

cond-mat.soft↗

arXiv2017

Connection between fragility, mean-squared displacement and shear modulus in two van der Waals bonded glass-forming liquids

The temperature dependence of the high-frequency shear modulus measured in the kHz range is compared to the mean-squared displacement measured in the nanosecond range for the two van der Waals bonded glass-forming liquids cumene and 5PPE. This provides an experimental test for the assumption connecting two versions of the shoving model for the non-Arrhenius temperature dependence of the relaxation time in glass formers. The two versions of the model are also tested directly and both are shown to work well for these liquids.

cond-mat.soft↗

arXiv2015

Thermotropic Orientational Order of Discotic Liquid Crystals in Nanochannels: An Optical Polarimetry Study and a Landau-de Gennes Analysis

Optical polarimetry measurements of the orientational order of a discotic liquid crystal based on a pyrene derivative and confined in parallel-aligned nanochannels of monolithic mesoporous alumina, silica, and silicon as a function of temperature, channel radius (3 - 22 nm) and surface chemistry reveal a competition of radial and axial columnar order. The evolution of the orientational order parameter of the confined systems is continuous, in contrast to the discontinuous transition in the bulk. For channel radii larger than 10 nm we suggest several, alternative defect structures, which are compatible both with the optical experiments on the collective molecular orientation presented here and with a translational, radial columnar order reported in previous diffraction studies. For smaller channel radii our observations can semi-quantitatively be described by a Landau-de Gennes model with a nematic shell of radially ordered columns (affected by elastic splay deformations) that coexists with an orientationally disordered, isotropic core. For these structures, the cylindrical phase boundaries are predicted to move from the channel walls to the channel centres upon cooling, and vice-versa upon heating, in accord with the pronounced cooling/heating hystereses observed and the scaling behavior of the transition temperatures with channel diameter. The absence of experimental hints of a paranematic state is consistent with a biquadratic coupling of the splay deformations to the order parameter.

cond-mat.soft↗

arXiv2013

Hyperfine interaction in CoCl$_2$ investigated by high resolution neutron spectroscopy

We investigated low energy nuclear spin excitations in the layered compound CoCl$_2$ by high resolution back-scattering neutron spectroscopy. We detected inelastic peaks at $E = 1.34 \pm 0.03$ $μ$eV on both energy loss and energy sides of the central elastic peak at $T = 2$ K. The energy of the inelastic peaks decrease with temperature continuously and become zero at $T_N \approx 25$ K at which the two ielastic peaks merge with the central elastic peak. We interpret the low energy excitations to be due to the transition between hyperfine field split nuclear levels. The present data together with the data on other Co compounds show that the energy of the nuclear spin excitations of a number of compounds follow a linear relationship with the electronic magnetic moment of the Co ion whereas that of other compounds deviate appreciably from this linear behaviour. We ascribe this anomalous behaviour to the presence of unquenched orbital moments of the Co ions.

cond-mat.mtrl-sci↗

arXiv2012

Magnetic ordering in double perovskites R$_2$CoMnO$_6$ (R= Y,Tb) investigated by high resolution neutron spectroscopy

We have investigated low energy nuclear spin excitations in double perovskite compounds R$_2$CoMnO$_6$ (R = Y,Tb) by inelastic neutron scattering with a high-resolution back-scattering spectrometer. We observed inelastic signals at about 2.1 $μ$eV for Y$_2$CoMnO$_6$ and also for Tb$_2$CoMnO$_6$ at T = 2 K in both energy loss and energy gain sides. We interpret these inelastic peaks to be due to the transitions between the hyperfine split nuclear levels of $^{59}$Co nucleus. The inelastic peaks move towards the central elastic peak and finally merge with it at the magnetic ordering temperature $T_C$. The energy of the low energy excitations decreases continuously and becomes zero at $T_C \approx 75$ K for Y$_2$CoMnO$_6$ and $T_C \approx 100$ K for Tb$_2$CoMnO$_6$. For Tb$_2$CoMnO$_6$, which contains magnetic rare-earth ions, additional quasielastic scattering due presumably to the fluctuations of large Tb magnetic moments was observed. The present study reveals the magnetic ordering of the Co sublattice. The results of this investigation along with that obtained by us for other compounds indicate the presence of unquenched orbital moments in some of the Co compounds.

cond-mat.str-el↗

arXiv2012

Molecular dynamics of n-hexane: A quasi-elastic neutron scattering study on the bulk and spatially nanochannel-confined liquid

We present incoherent quasi-elastic neutron scattering measurements in a wavevector transfer range from 0.4 AA^{-1} to 1.6AA^{-1} on liquid n-hexane confined in cylindrical, parallel-aligned nanochannels of 6 nm mean diameter and 260 micrometer length in monolithic, mesoporous silicon. They are complemented with, and compared to, measurements on the bulk system in a temperature range from 50K to 250K. The time-of-flight spectra of the bulk liquid can be modeled by microscopic translational as well as fast localized rotational, thermally-excited, stochastic motions of the molecules. In the nano-confined state of the liquid, which was prepared by vapor condensation, we find two molecular populations with distinct dynamics, a fraction which is immobile on the time scale of 1ps to 100ps probed in our experiments and a second component with a self-diffusion dynamics slightly slower than observed for the bulk liquid. No hints of an anisotropy of the translational diffusion with regard to the orientation of the channels' long axes have been found. The immobile fraction amounts to about 5% at 250K, gradually increases upon cooling and exhibits an abrupt increase at 160K (20K below bulk crystallization), which indicates pore freezing

cond-mat.soft↗

arXiv2009

Relation between static short-range order and dynamic heterogeneities in a nanoconfined liquid crystal

We analyze the molecular dynamics heterogeneity of the liquid crystal 4-n-octyl-4'-cyanobiphenyl nanoconfined in porous silicon. We show that the temperature dependence of the dynamic correlation length ?wall, which measures the distance over which a memory of the interfacial slowing down of the molecular dynamics persists, is closely related to the growth of the short-range static order arising from quenched random fields. More generally, this result may also shed some light on the connection between static and dynamic heterogeneities in a wide class of condensed and soft matter systems.

physics.chem-ph↗

arXiv2009

Bioprotectant glassforming solutions confined in porous silicon nanocapillaries

Glycerol and trehalose-glycerol binary solutions are glass-forming liquids with remarkable bioprotectant properties. In this paper, we address the effects of confining of these solutions in straight channels of diameter D=8 nm formed by porous silicon. Neutron diffraction and incoherent quasielastic neutron scattering are used to reveal the different effects of nanoconfinement and addition of trehalose on the intermolecular structure and molecular dynamics of the liquid and glassy phases, on a nanosecond timescale.

cond-mat.soft↗

arXiv2009

Molecular dynamics of glycerol and glycerol-trehalose bioprotectant solutions nanoconfined in porous silicon

Glycerol and trehalose-glycerol binary solutions are glass-forming liquids with remarkable bioprotectant properties. Incoherent quasielastic neutron scattering (QENS) is used to reveal the different effects of nanoconfinement and addition of trehalose on the molecular dynamics in the normal liquid and supercooled liquid phases, on a nanosecond timescale. Confinement has been realized in straight channels of diameter D=8 nm formed by porous silicon. It leads to a faster and more inhomogeneous relaxation dynamics deep in the liquid phase. This confinement effect remains at lower temperature where it affects the glassy dynamics. The glass transitions of the confined systems are shifted to low temperature with respect to the bulk ones. Adding trehalose tends to slow down the overall glassy dynamics and increases the non-exponential character of the structural relaxation. Unprecedented results are obtained for the binary bioprotectant solution, which exhibits an extremely non-Debye relaxation dynamics as a result of the combination of the effects of confinement and mixing of two constituents.

cond-mat.soft↗

arXiv2008

Incoherent Quasielastic Neutron Scattering Study of Molecular dynamics of 4-n-cyano-4'-octylbiphenyl

We report incoherent quasielastic neutron scattering experiments on the thermotropic liquid crystal 4-n-cyano-4'-octylbiphenyl. The combination of time-of-flight and backscattering data allows analyzing the intermediate scattering function over about three decades of relaxation times. Translational diffusion and uniaxial molecular rotations are clearly identified as the major relaxation processes in respectively the nanosecond and picosecond time scales. The comparison with literature data obtained by other techniques is discussed.

physics.chem-ph↗

arXiv2006

Molecular dynamics of a short range ordered smectic phase nanoconfined into porous silicon

4-n-octyl-4-cyanobiphenyl (8CB) has been recently shown to display an unusual sequence of phases when confined into porous silicon (PSi). The gradual increase of oriented short-range smectic (SRS) correlations in place of a phase transition has been interpreted as a consequence of the anisotropic quenched disorder induced by confinement in PSi. Combining two quasielastic neutron scattering experiments with complementary energy resolutions, we present the first investigation of the individual molecular dynamics of this system. A large reduction of the molecular dynamics is observed in the confined liquid phase, as a direct consequence of the dynamical boundary conditions imposed by the confinement. Temperature fixed window scans (FWS) reveal a continuous 'glass-like' reduction of the molecular dynamics of the confined liquid and SRS phases on cooling down to 250 K, where a solid-like behavior is finally reached by a two steps crystallization process.

cond-mat.mtrl-sci↗

arXiv2006

Dynamics of 8CB confined into porous silicon probed by incoherent neutron backscattering experiments

Confinement in the nanochannels of porous silicon strongly affects the phase behavior of the archetype liquid-crystal 4-n-octyl-4-cyanobiphenyl (8CB). A very striking phenom- enon is the development of a short-range smectic order, which occurs on a very broad temperature range. It suggests in this case that quenched disorder effects add to usual finite size and surface interaction effects. We have monitored the temperature variation of the molecular dynamics of the confined fluid by incoherent quasielastic neutron scat- tering. A strongly reduced mobility is observed at the highest temperatures in the liquid phase, which suggests that the interfacial molecular dynamics is strongly hindered. A continuously increasing slowdown appears on cooling together with a progressive growth of the static correlation length

cond-mat.soft↗