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Damian Pociecha

Publications and source records attributed to Damian Pociecha.

At least 19 recordsLinked to original sources

Mirror vs. inversion symmetry breaking in mesogenic dimers: NTB vs. NF phase

The recently discovered twist-bend nematic NTB and ferroelectric nematic NF phases are distinct examples of spontaneous symmetry breaking in liquid crystals. Here, we report the occurrence of both type nematic phases within the same homologous series of dimers consisting of two strongly dipolar mesogenic units linked by a flexible spacer. The NF phase, observed for dimers having spacer with even number of atoms, exhibits the strong polar order; in the NTB phase, observed for dimers with odd number of atoms in the spacer, short-pitch heliconical director structure develops.

cond-mat.soft

Competing ferroelectric and smectic order: modulated structures through molecular design

We demonstrate that the balance between polar and positional order can be systematically tuned through molecular engineering, providing direct control over the emergence of polar and modulated liquid-crystalline phases, allowing for versatile strategy for the design of functional ferroelectric soft materials. We show that polar orthogonal smectic phases (SmAF and SmAAF), promoted by the self-segregation of aromatic cores and sufficiently long terminal chains, are readily destabilized by strong longitudinal dipolar interactions that energetically penalize parallel alignment of molecular dipoles within a smectic layer. In contrast, the tilted ferroelectric SmCF phase is remarkably robust across the entire homologous series, indicating that molecular tilt efficiently relieves dipolar frustration within the smectic layers. We further demonstrate that the interplay between microsegregation and electrostatic interactions stabilizes the new modulated SmCM phase, characterized by incommensurate electron-density waves, particularly for compounds with short terminal chains. For longer homologs controlling the spatial distribution of fluorinated molecular fragments and terminal-chain length enabled the targeted formation of broken-layer-type modulated polar phases (2D or 3D).

cond-mat.soft

Helix alignment, chevrons, and edge dislocations in twist-bend ferroelectric nematics

We explore surface alignment and edge dislocations in the recently discovered twist-bend ferroelectric nematic, NTBF, in which the vector of spontaneous polarization follows an oblique helicoidal trajectory around a polar twist-bend axis. In a planar cell, the polar axis aligns at some angle to the rubbing direction to mitigate surface electric charge. We demonstrate that the pseudolayers in planar cells form chevron defects, a hallmark defect of one-dimensionally positionally ordered phases, such as smectic A and smectic C. The polar character of the twist-bend axis prevents the cores of NTBF edge dislocations from splitting into semi-integer disclinations, in stark contrast to dislocations in paraelectric and ferroelectric chiral nematics. The tilt of pseudolayers around the defect core allows us to estimate the elastic penetration length as being close to the pitch of NTBF. Compression/dilation stresses around the core modify the heliconical tilt angle of molecules as evidenced by a substantial variation in local birefringence. The climb of dislocations exhibits high mobility, allowing the system to equilibrate the temperature-dependent pitch. The uncovered properties facilitate the development of NTBF materials for electro-optical applications, such as electrically controlled diffraction lattices and structural colors.

cond-mat.soft

Competition between mirror symmetry breaking and translation symmetry breaking in ferroelectric liquid crystals with increasing lateral substitution

The recently discovered heliconical ferroelectric nematic (NTBF) phase is a unique example of spontaneous chiral symmetry breaking in a proper ferroelectric fluid. In this study, we investigate four homologous series of mesogenic compounds, differing in the degree of fluorination of the mesogenic core and bearing lateral alkoxy substituents of varying lengths, to understand how molecular architecture influences the formation and stability of the NTBF phase. Increasing the length of the lateral chain lowers the phase transition temperatures and suppresses smectic layer formation, enabling the emergence of the NTBF phase which replaces the orthogonal ferroelectric smectic A (SmAF) phase. This indicates a competition between lamellar and heliconical polar ordering, driven by the interplay of strong molecular dipoles and the self-segregation of chemically incompatible molecular segments that typically favor layered structures. Notably, the NTBF phase in these compounds exhibits exceptionally short helical pitch lengths, on the order of a few hundred nanometers, as revealed by selective light reflection and atomic force microscopy (AFM). Furthermore, for one of the studied compounds AFM imaging of one compound revealed a regular array of screw dislocations within the NTBF phase, suggesting a possible link to more complex modulated or twist-grain-boundary-like structures.

cond-mat.soft

Interplay of polar order and positional order in liquid crystals -- observation of re-entrant ferroelectric nematic phase

We show that development of polar order may spontaneously destroy the lamellar structure of a liquid crystal. This results in an unusual sequence of phases with the ferroelectric nematic phase appearing below a non-polar smectic phase. The effect is related to unfavourable dipole interactions within the smectic layers and can be explained by Landau theory in which the temperature dependent term is non-monotonic as it is renormalized by spontaneous electric polarization.

cond-mat.soft

Twist Grain Boundary phases in proper ferroelectric liquid crystals realm

The twist-grain-boundary (TGB) phases, characterized by a periodic, helical arrangement of blocks made of polar smectic phases, SmAF and SmCF, have been discovered. They have been observed for rod-like molecules with a strong longitudinal dipole moment, featuring an (S)-2-methylbutyl end group having only weak twisting power, and emerge below the antiferroelectric SmAAF phase, where the lamellar structure is already well established. It is suggested that the structure is governed by electrostatic interactions amplified by weak chiral forces, in striking contrast to the mechanism of TGB phase formation found in non-polar materials. The TGB phases exhibit light selective reflection in the visible range, while the value of electric polarization confirms an almost perfectly ordered dipole alignment.

cond-mat.soft

The role of terminal groups in non-chiral rod-like compounds on the formation of polar fluids

The emergence of ferroelectric mesophases in non-chiral liquid crystal (LCs) has sparked fundamental interest in the molecular mechanisms governing polarity. In this study, we investigate how terminal molecular groups influence the formation and stability of polar phases by analyzing six compounds from three homologous series. Specifically, we compare newly synthesized homologs with a nitro group, which predominantly exhibit polar mesophases, to previously reported structurally related analogs containing either a cyano group or a fluorine atom as terminal fragment. Density Functional Theory (DFT) calculations provide insights into electronic surface potential (ESP) distributions, revealing alternating regions of positive and negative charge density along the molecular axis, consistent with Madhusudana model of polar phase stabilization. We propose the ESP-derived parameter quantifying terminal electrostatic charge, revealing a direct correlation between the negative to positive charge ratio at the molecular termini and the formation of ferroelectric or antiferroelectric mesophases. To validate this hypothesis, we analyze the molecular structure-mesomorphic behavior relationship of other known non-chiral compounds that exhibit polar phases, demonstrating the critical role of terminal groups in determining mesophase polarity. Our findings enhance the understanding of the molecular origins of ferroelectricity in non-chiral LCs, paving the way for the rational design of next-generation functional polar soft materials.

cond-mat.mtrl-sci

The balance between paraelectricity and ferroelectricity in non-chiral smectic homologs

Non-chiral liquid crystals (LCs) exhibiting ferroelectricity, distinguished by their dynamic responsiveness to external stimuli and high spontaneous polarization, provide renewed impetus for research into this area of soft matter and open novel application possibilities. Consequently, identifying structural elements within LC compounds that promote ferroelectricity in non-chiral systems is of critical importance. In this work, two homologs of rod-like compounds, with phenyl and ester groups in the rigid core substituted by fluorine atoms, differing by a single methylene unit, were synthesized and comprehensively analyzed using complementary experimental techniques and quantum-mechanical modeling. This systematic study presents the first documented instance in which such a minimal structural modification markedly influences the polarity of smectic phases in two homologs, without substantially altering phase transition temperatures, particularly the sequence and temperature ranges of smectic and nematic phases. Additionally, findings reveal that the longer homolog, which exhibits paraelectric phases, demonstrates a pronounced capacity to maintain ferroelectric phases in mixtures. These results provide new insights into the critical structure-property relationships between molecular architecture and ferroelectric characteristics in LCs, facilitating the targeted design of non-chiral compounds with polar phases. Moreover, the properties of the studied mixtures underscore the potential to develop multicomponent LC mixtures with stable ferroelectric properties in a broad temperature range, a feature of considerable significance for practical applications.

cond-mat.mtrl-sci

Spontaneous polar and chiral symmetry breaking in ordered fluids -- heliconical ferroelectric nematic phases

It is known that the chiral interaction described by Dzyaloshinskii-Moriya (DMI) term lead to the plethora of topological structures of magnetic spins, such as helical or skyrmion phases. Here we present the that analogues electrical DMI can lead to similar structural complexity of electric dipoles in soft matter. We report on a new polar liquid phase in which achiral molecules spontaneously form a heliconical structure. The helical pitch is comparable to the wavelength of visible light and unwinds critically at the transition to a uniformly polar, ferroelectric nematic phase. Although this new liquid crystalline phase resembles the twist-bend nematic phase, the mechanism of its formation is different and is attributed to electrical interactions that cause non-collinear arrangement of electric dipoles, similarly as observed for spins in magnetic systems.

cond-mat.soft

Spontaneous helix formation in polar smectic phase

In soft ferroelectric crystals, the depolarization field can be reduced by periodic distortion of the polarization direction. In the polar nematic and tilted smectic phases, this process is energetically favorured , as it only requires changes in the director orientation. We demonstrate the spontaneous formation of a helical structure in the proper ferroelectric tilted smectic (SmCTBF) phase, the phase is formed below the heliconical polar nematic (NTBF) phase. The helical pitch in the smectic phase is approximately 600 nm and remains nearly constant across the entire temperature range of the phase. Under weak electric fields, the helix reorients while its structure remains largely intact; however, in stronger fields, the helix is destroyed as the electric polarization aligns along the electric field.

cond-mat.soft

Ferroelectric nematics: Materials with high permittivity or low resistivity?

Two models have recently been proposed for a description of dielectric spectroscopy measurements of ferroelectric nematics (NF) in thin planar capacitors. The polarization-external capacitance Goldstone reorientation mode (PCG model) considers the NF layer between the electrodes as an effective low resistivity material, the resistivity being inversely proportional to the square of polarisation magnitude. The high-ε model considers the NF material as having a huge permittivity due to the ease of polarisation rotation. In this paper we study implications of both models and show, why both models describe majority of the observed dielectric spectroscopy results equally well. We point out differences among the models predictions and explain why some observations can be explained only by the high-ε model. The major difference between the models is that the high-ε model predicts that the increase in the cell thickness can lead to an increase in the frequency range within which capacitors filled with NF material can be used for energy storage while within the PCG model this frequency range reduces with increasing capacitor thickness. Within both models a crucial parameter which determines the behaviour of the capacitors filled with a NF material is parasitic resistance, primarily due to the electrode resistance. We present measurements of electrode resistance and find that in ITO cells it is of the order of few hundred ohms.

cond-mat.mtrl-sci

Nematic and smectic phases with proper ferroelectric order

A material showing a sequence of three ferroelectric liquid crystalline phases below the paraelectric nematic phase has been synthesized and studied. The polar order of molecules appearing due to the dipole-dipole interactions in the NF phase is preserved also in the smectic phases: orthogonal SmAF and tilted SmCF. The ferroelectric ground state of both smectic phases is confirmed by their second harmonic generation activity and polarization switching. In the SmCF phase the polarization becomes oriented to the electric field by decreasing the tilt angle to zero. Although both smectic phases are ferroelectric in nature, their dielectric response is found to be very different.

cond-mat.soft

Interpretation of dielectric spectroscopy measurements of ferroelectric nematic liquid crystals

The magnitude of the relative permittivity of the ferroelectric nematic phase (NF) is under a lively scientific discussion since the phase was recently discovered. Dielectric spectroscopy measurements (DSM) give a huge value of relative permittivity, which depends on the cell thickness, but this is argued to result from a misinterpretation of the DSM results. We have conducted DSM using a set of cells differing in thickness of the NF layer, type of electrodes and presence/absence of nanoscale-thick surface layers. To model the DSM results, cells are presented by an equivalent electric circuit that includes a capacitor due to the NF layer with frequency dependent complex relative permittivity, capacitors due to surface layers, and a resistor describing limited conductivity of electrodes. DSM results for different cells with the same liquid crystal in the NF phase, are semi-quantitatively reproduced by the same set of physical parameters if a huge relative permittivity of the NF, which is even orders of magnitude larger than the measured apparent values, is assumed. We show that the capacitance of surface layers should be considered also in cells with no polymer alignment layer on electrodes.

cond-mat.soft

Polar order in a fluid like ferroelectric with a tilted lamellar structure -- observation of a polar smectic C (SmC${_\textrm{P}}$) phase

The discovery of fluid states of matter with spontaneous bulk polar order is appreciated as a major discovery in the fields of soft matter and liquid crystals. Typically, this manifests as polar order superimposed atop conventional phase structures and is thus far limited to orthogonal phase types. Here we report a family of materials which exhibit a previously unseen state of matter which we conclude is a polar smectic C phase, and so we term it SmC${_\textrm{P}}$. The spontaneous polarisation of the SmC${_\textrm{P}}$ phase is over two orders of magnitude larger than that found in conventional ferroelectric SmC phase of chiral materials used in some LCD devices. Fully atomistic molecular dynamics simulations faithfully and spontaneously reproduce the proposed structure and associated bulk properties; comparison of experimental and simulated X-ray scattering patterns shows excellent agreement. The materials disclosed here have significantly smaller dipole moments than typical polar liquid crystals such as RM734 which suggests the role of molecular electrical polarity in generating polar order is perhaps overstated, a view supported by consideration of other molecular systems.

cond-mat.soft

Ferroelectric nematic -- isotropic critical end point

A critical end point above which an isotropic phase continuously evolves into a polar (ferroelectric) nematic phase with an increasing electric field is found in a ferroelectric nematic liquid crystalline material. The critical end point is approximately 30 K above the zero-field transition temperature from the isotropic to nematic phase and at an electric field of the order of 10 V/micron. Such systems are interesting from the application point of view because a strong birefringence can be induced in a broad temperature range in an optically isotropic phase.

cond-mat.soft

Tilt or twist-competing synclinic and anticlinic interactions in SmC phases of bent-core mesogens

Recent liquid-crystalline (LC) research is focused on structurally new molecular systems distinct from simple nematic or smectic phases. Sophisticated molecular shape may reveal structural complexity, combining helicity and polarity. Achiral symmetry-breaking in bent-core molecules leads to propensity for synclinic and anticlinic molecular structures within consecutive smectic layers. Moreover, despite their achiral character, dimers readily adopt helical phases. In our study, we investigated a hybrid molecular structure incorporating both characteristics, namely a rigid-bent core and an attached bulky polar group via a flexible spacer. To perform phase identification, we enriched the standard experimental methods with the sophisticated resonant soft x-ray scattering. Notably, we have observed a distinct preference for specific phase types depending on the length of the homologue. Longer homologues exhibit a predisposition towards the formation of tilted smectic phases, characterized by complex sequences of synclinic and anticlinic interfaces. Conversely, shorter homologues manifest a propensity for helical smectic structures. For intermediate homologues, the frustration is alleviated through the formation of several modulated smectic phases. Based on the presented research, we describe the preconditions for high level structures in relation with conflicting constraints.

cond-mat.soft

To be or not to be polar: the ferroelectric and antiferroelectric nematic phases

We report the properties of two new series of compounds that show the ferroelectric nematic phase in which the length of a terminal chain is varied. The longer the terminal chain, the weaker the dipole-dipole interactions of the molecules are along the director, and thus the lower the temperature at which the axially ferroelectric nematic phase is formed. For homologues of intermediate chain length, between the non-polar and ferroelectric nematic phases, there is a wide temperature range nematic phase with antiferroelectric character. The size of the antiparallel ferroelectric domains critically increases upon transition to the ferroelectric phase. In dielectric studies, both collective ("ferroelectric" and non-collective fluctuations are present, the "ferroelectric" mode softens weakly at the N-NX phase transition because the polar order in this phase is weak. The transition to the NF phase is characterized by a much stronger lowering of the mode relaxation frequency and an increase in its strength, typical critical behavior is observed.

cond-mat.soft

Dielectric response of a ferroelectric nematic liquid crystalline phase in thin cells

We studied dielectric properties of a polar nematic phase (NF) sandwiched between two gold or ITO electrodes, serving as a cell surfaces. In bulk, NF is expected to exhibit a Goldstone mode (phason), because polarization can uniformly rotate with no energy cost. However, because the coupling between the direction of nematic director and polarization is finite, and the confinement, even in the absence of the aligning surface layer, induces some energy cost for a reorientation of polarization, the phason dielectric relaxation frequency is measured in a kHz regime. The phason mode is easily quenched by a bias electric field, which enables fluctuations in the magnitude of polarization to be followed in both, the ferronematic and nematic phases. This amplitude (soft) mode is also influenced by boundary conditions. A theory describing the phase and amplitude fluctuations in the NF phase shows that the free energy of the system and, consequently, the dielectric response are dominated by polarization-related terms with the flexoelectricity being relevant only at a very weak surface anchoring. Contributions due to the nematic elastic terms are always negligible. The model relates the observed low frequency mode to the director fluctuations weakly coupled to polarization fluctuations.

cond-mat.soft