Macroscopic Order Research Articles

A multiscale approach to uncover the self-assembly of ligand-covered palladium nanocubes.

Ligand-mediated superlattice assemblies of metallic nanocrystals represent a new type of mesoscale materials whose structural ordering directly influence emergent collective properties. However, universal control over the spatial and orientational ordering of their constitutive components remains an open challenge. One major barrier contributing to the lack of programmability in these nanoscale building blocks revolves around a gap in fundamental understanding of how ligand-mediated interactions at the particle level propagate to macroscopic and mesoscale behaviors. Here, we employ a combination of scaling theory and coarse-grained simulations to develop a multiscale modeling framework capable of bridging across hierarchical assembly length scales for a model system of ligand-functionalized nanocubes (here, Pd). We first employ atomistic simulations to characterize how specific ligand-ligand interactions influence the local behaviors between neighboring Pd nanocubes. We then utilize a mean-field scaling theory to both rationalize the observed behaviors as well as compute a coarse-grained effective pairwise potential between nanocubes capable of reproducing atomistic behaviors at the mesoscale. Furthermore, our simulations reveal that a complex interplay between ligand-ligand interactions is directly responsible for a shift in macroscopic ordering between neighboring nanocubes. Our results, therefore, provides a critical step forward in establishing a multiscale understanding of ligand-functionalized nanocrystalline assemblies that can be subsequently leveraged to design targeted structures exhibiting novel, emergent collective properties.

Abrupt desynchronization and abrupt transition to [formula omitted]-state in globally coupled oscillator simplexes with contrarians and conformists

We study the phase transitions in a generalized Kuramoto model with contrarians and conformists along with a higher order coupling encoded simplex. Incoherent state persists for a large fraction of contrarians, while there is a continuous transition from the former to π-state and traveling wave state as the fraction of conformists increases under the high proportion of the pair-wise coupling and for a higher coupling strength of the conformists than contrarians. Hong and Strogatz (2011) showed the abrupt transition to the π-state when the contrarians coupling strength supersede in a purely pair-wise coupling. A large proportion of higher order coupling induces the abrupt transition to the π-state even when the contrarians coupling strength is feeble than that of the conformists, destabilizes the traveling wave state, and stabilizes the incoherent state in the entire phase diagram despite the presence of a large fraction of the conformists, which coexists with the π-state. Consequently, one can observe an abrupt desynchronization transition to the incoherent state during the backward trace, while the system remains in the incoherent state during the forward trace. The range of the bistable region between the incoherent state and the π-state increases with the proportion of the higher order coupling to a maximum until the abrupt transition to the π-state ceases to exist. We deduce the pitchfork and saddle–node bifurcation curves across which the incoherent state and the π-state lose their stability from the evolution equation for the low-dimensional dynamics corresponding to the macroscopic order parameters.

Development of nanosilver embedded injectable liquid crystalline hydrogel from alginate and chitosan for potent antibacterial and anticancer applications

Injectable hydrogels with macroscopic ordering have gained special attention in drug delivery due to their excellent biocompatibility and minimally invasive surgical procedure. Nanosilver embedded Schiff base hydrogel from biopolymers alginate and chitosan was developed and demonstrated its application in the injectable delivery of anticancer drug Dox.HCl. The ordered hydrogel structure was evidenced by FT-IR, DLS, XRD and Rheology. The self-assembled morphology of nanosilver- Schiff base hydrogels was studied by microscopic techniques such as SEM, TEM and AFM. The pH dependent anticancer activity of the hydrogel was demonstrated by invitro drug release studies at pH 5.5 and 86.56 % release was obtained for 100 mgL-1 of Dox.HCl loaded hydrogel at 72 hours. The antibacterial activity attained from nanosilver can be assessed by Agar well diffusion assay and minimum inhibitory concentration and minimum biocidal concentrations were determined as 62.5 μL/mL and 125 μL/mL, respectively. The invitro cell viability studies were done against skin cancer cell B16 by MTT assay which shows 34.82 % of toxicity towards B16 cancer cells and the cell death was further confirmed by Apoptosis assay and flow cytometry. The developed macroscopically ordered liquid crystalline hydrogel can be act as a versatile platform for injectable drug delivery system.

Inferring couplings in networks across order-disorder phase transitions.

Statistical inference is central to many scientific endeavors, yet how it works remains unresolved. Answering this requires a quantitative understanding of the intrinsic interplay between statistical models, inference methods, and the structure in the data. To this end, we characterize the efficacy of direct coupling analysis (DCA) - a highly successful method for analyzing amino acid sequence data-in inferring pairwise interactions from samples of ferromagnetic Ising models on random graphs. Our approach allows for physically motivated exploration of qualitatively distinct data regimes separated by phase transitions. We show that inference quality depends strongly on the nature of data-generating distributions: optimal accuracy occurs at an intermediate temperature where the detrimental effects from macroscopic order and thermal noise are minimal. Importantly our results indicate that DCA does not always outperform its local-statistics-based predecessors; while DCA excels at low temperatures, it becomes inferior to simple correlation thresholding at virtually all temperatures when data are limited. Our findings offer insights into the regime in which DCA operates so successfully, and more broadly, how inference interacts with the structure in the data.

Comment on "Improper molecular ferroelectrics with simultaneous ultrahigh pyroelectricity and figures of merit" by Li et al.

Li et al. (Science Advances, 29 January, p. eabe3068) claim the discovery of two improper ferroelectrics, dabcoHClO4 and dabcoHBF4 (dabco = 1,4-diazabicyclo[2.2.2]octane), and that these materials exhibit superior pyroelectric figures of merit. This information is misleading because of the fundamental methodological errors and false conclusions, not to mention that these ferroelectrics were reported more than 20 years ago. They are proper ferroelectrics, for which the spontaneous polarization is the macroscopic order parameter. We show that the useful pyroelectric coefficients of dabcoHClO4 and dabcoHBF4 are about 1000 times lower than the coefficients reported by Li et al.

Ultrafast kinetics of the antiferromagnetic-ferromagnetic phase transition in FeRh

Understanding how fast short-range interactions build up long-range order is one of the most intriguing topics in condensed matter physics. FeRh is a test specimen for studying this problem in magnetism, where the microscopic spin-spin exchange interaction is ultimately responsible for either ferro- or antiferromagnetic macroscopic order. Femtosecond laser excitation can induce ferromagnetism in antiferromagnetic FeRh, but the mechanism and dynamics of this transition are topics of intense debates. Employing double-pump THz emission spectroscopy has enabled us to dramatically increase the temporal detection window of THz emission probes of transient states without sacrificing any loss of resolution or sensitivity. It allows us to study the kinetics of emergent ferromagnetism from the femtosecond up to the nanosecond timescales in FeRh/Pt bilayers. Our results strongly suggest a latency period between the initial pump-excitation and the emission of THz radiation by ferromagnetic nuclei.

Emergent pseudo time-irreversibility in the classical many-body system of pair interacting particles

In this paper, the emergence of macroscopic-scale pseudo time-irreversibility is studied in the closed classical many-body system of pair interacting particles. First, exact continuum equations are derived to the Hamiltonian dynamics without the utilisation of statistical mechanics. Next, it is shown that the momentum density field incorporates the thermal degrees of freedom in the considered scaling limit, and therefore initial condition indicated pseudo time-irreversible solutions may exist to the dynamical equations. Numerical evidence for pseudo-irreversible thermal equilibration, heat and momentum transport is provided. Finally, the possible reasons of the numerically obtained non-diffusional relaxation of macroscopic order is discussed.

Exact solution of a boundary time-crystal phase transition: Time-translation symmetry breaking and non-Markovian dynamics of correlations

The breaking of the continuous time-translation symmetry manifests, in Markovian open quantum systems, through the emergence of non-stationary dynamical phases. Systems that display nonequilibrium transitions into these phases are referred to as time-crystals, and they can be realized, for example, in many-body systems governed by collective dissipation and long-ranged interactions. Here, we provide a complete analytical characterization of a boundary time-crystal phase transition. This involves exact expressions for the order parameter and for the dynamics of quantum fluctuations, which, in the time-crystalline phase, remains asymptotically non-Markovian as a consequence of the time-translation symmetry breaking. We demonstrate that boundary time-crystals are intrinsically critical phases, where fluctuations exhibit a power-law divergence with time. Our results show that a dissipative time-crystal phase is far more than merely a classical non-linear and non-stationary (limit cycle) dynamics of a macroscopic order parameter. It is rather a genuine many-body phase where the properties of correlations distinctly differs from that of stationary ones.

Influence of asymmetric parameters in higher-order coupling with bimodal frequency distribution.

We investigate the phase diagram of the Sakaguchi-Kuramoto model with a higher-order interaction along with the traditional pairwise interaction. We also introduce asymmetry parameters in both the interaction terms and investigate the collective dynamics and their transitions in the phase diagrams under both unimodal and bimodal frequency distributions. We deduce the evolution equationsfor the macroscopic order parameters and eventually derive pitchfork and Hopf bifurcation curves. Transition from the incoherent state to standing wave pattern is observed in the presence of the unimodal frequency distribution. In contrast, a rich variety of dynamical states such as the incoherent state, partially synchronized state-I, partially synchronized state-II, and standing wave patterns and transitions among them are observed in the phase diagram via various bifurcation scenarios, including saddle-node and homoclinic bifurcations, in the presence of bimodal frequency distribution. Higher-order coupling enhances the spread of the bistable regions in the phase diagrams and also leads to the manifestation of bistability between incoherent and partially synchronized states even with unimodal frequency distribution, which is otherwise not observed with the pairwise coupling. Further, the asymmetry parameters facilitate the onset of several bistable and multistable regions in the phase diagrams. Very large values of the asymmetry parameters allow the phase diagrams to admit only the monostable dynamical states.

Quantifying Order during Field-Driven Alignment of Colloidal Semiconductor Nanorods.

Aligning large populations of colloidal nanorods (NRs) into ordered assemblies provides a strategy for engineering macroscopic functional materials with strong optical anisotropy. The bulk optical properties of such systems depend not only on the individual NR building blocks but also on their meso- and macroscale ordering, in addition to more complex interparticle coupling effects. Here, we investigate the dynamic alignment of colloidal CdSe/CdS NRs in the presence of AC electric fields by measuring concurrent changes in optical transmission. Our work identifies two distinct scales of interaction that give rise to the field-driven optical response: (1) the spontaneous mesoscale self-assembly of colloidal NRs into structures with increased optical anisotropy and (2) the macroscopic ordering of NR assemblies along the direction of the applied AC field. By modeling the alignment of NR ensembles using directional statistics, we experimentally quantify the maximum degree of order in terms of the average deviation angle relative to the field axis. Results show a consistent improvement in alignment as a function of NR concentration─with a minimum average deviation of 36.2°─indicating that mesoscale assembly helps facilitate field-driven alignment of colloidal NRs.

Non-Normal Interactions Create Socio-Economic Bubbles

We present a generic new mechanism for the emergence of collective exuberance among interacting agents in a general class of Ising-like models that have a long history in social sciences and economics. The mechanism relies on the recognition that socio-economic networks are intrinsically non-symmetric and hierarchically organized, which is represented as a non-normal adjacency matrix. Such non-normal networks lead to transient explosive growth in a generic domain of control parameters, in particular in the subcritical regime. Contrary to previous models, here the coordination of opinions and actions and the associated global macroscopic order do not require the fine-tuning close to a critical point. This is illustrated in the context of financial markets theoretically, numerically via agent-based simulations and empirically through the analysis of so-called meme stocks. It is shown that the size of the bubble is directly controlled through the Kreiss constant which measures the degree of non-normality in the network. This mapping improves conceptually and operationally on existing methods aimed at anticipating critical phase transitions, which do not take into consideration the ubiquitous non-normality of complex system dynamics. Our mechanism thus provides a general alternative to the previous understanding of instabilities in a large class of complex systems, ranging from ecological systems to social opinion dynamics and financial markets.

Exact dynamics of phase transitions in oscillator populations with nonlinear coupling

The Kuramoto model consisting of a population of coupled phase oscillators has served as an idealized tool for studying synchronization transitions in diverse self-sustained systems. It has been a common brief that the model exhibits a first-order discontinuous (hybrid) phase transition towards synchrony with the absence of partial locking by assuming that the natural frequencies are uniformly distributed. In this paper, we consider a variant of this model by modifying its global coupling to depend on a power law function of the macroscopic order parameter of the population via an exponent α. The generalization retains the uniform coupling and mean-field character of the system, where there is an interplay between the coupling and oscillator dynamics. Surprisingly, we show that the partial locking with the coexistence of the phase locked and drifting populations indeed exists for α<1, whereas it can never occur as long as α≥1. Through a remarkable ansatz of the frequency-dependent version of Ott–Antonsen manifold, we reveal that the long term macroscopic dynamics of the resulting model, as well as their corresponding critical properties can be analytically described. More importantly, we construct the characteristic function to give intuitive interpretations of a variety of dynamical phenomena occurring in the system, such as the emergence of the partial locking, vanishing synchronization onset, and the irreversibly abrupt desynchronization transition.

Snowdrift game induces pattern formation in systems of self-propelled particles.

Evolutionary games between species are known to lead to intriguing spatiotemporal patterns in systems of diffusing agents. However, the role of interspecies interactions is hardly studied when agents are (self-)propelled, as is the case in many biological systems. Here, we combine aspects from active matter and evolutionary game theory and study a system of two species whose individuals are (self-)propelled and interact through a snowdrift game. We derive hydrodynamic equations for the density and velocity fields of both species from which we identify parameter regimes in which one or both species form macroscopic orientational order as well as regimes of propagating wave patterns. Interestingly, we find simultaneous wave patterns in both species that result from the interplay between alignment and snowdrift interactions-a feedback mechanism that we call game-induced pattern formation. We test these results in agent-based simulations and confirm the different regimes of order and spatiotemporal patterns as well as game-induced pattern formation.

Subpicosecond metamagnetic phase transition in FeRh driven by non-equilibrium electron dynamics

Femtosecond light-induced phase transitions between different macroscopic orders provide the possibility to tune the functional properties of condensed matter on ultrafast timescales. In first-order phase transitions, transient non-equilibrium phases and inherent phase coexistence often preclude non-ambiguous detection of transition precursors and their temporal onset. Here, we present a study combining time-resolved photoelectron spectroscopy and ab-initio electron dynamics calculations elucidating the transient subpicosecond processes governing the photoinduced generation of ferromagnetic order in antiferromagnetic FeRh. The transient photoemission spectra are accounted for by assuming that not only the occupation of electronic states is modified during the photoexcitation process. Instead, the photo-generated non-thermal distribution of electrons modifies the electronic band structure. The ferromagnetic phase of FeRh, characterized by a minority band near the Fermi energy, is established 350 ± 30 fs after the laser excitation. Ab-initio calculations indicate that the phase transition is initiated by a photoinduced Rh-to-Fe charge transfer.

Multidimensional Nano-Imaging of Structure, Coupling, and Disorder in Molecular Materials.

A hierarchy of intramolecular and intermolecular interactions controls the properties of biomedical, photophysical, and novel energy materials. However, multiscale heterogeneities often obfuscate the relationship between microscopic structure and emergent function, and they are generally difficult to access with conventional optical and electron microscopy techniques. Here, we combine vibrational exciton nanoimaging in variable-temperature near-field optical microscopy (IR s-SNOM) with four-dimensional scanning transmission electron microscopy (4D-STEM), and vibrational exciton modeling based on density functional theory (DFT), to link local microscopic molecular interactions to macroscopic three-dimensional order. In the application to poly(tetrafluoroethylene) (PTFE), large spatio-spectral heterogeneities with C-F vibrational energy shifts ranging from sub-cm-1 to ≳25 cm-1 serve as a molecular ruler of the degree of local crystallinity and disorder. Spatio-spectral-structural correlations reveal a previously invisible degree of highly variable local disorder in molecular coupling as the possible missing link between nanoscale morphology and associated electronic, photonic, and other functional properties of molecular materials.

Polar in-plane surface orientation of a ferroelectric nematic liquid crystal: Polar monodomains and twisted state electro-optics

We show that surface interactions can vectorially structure the three-dimensional polarization field of a ferroelectric fluid. The contact between a ferroelectric nematic liquid crystal and a surface with in-plane polarity generates a preferred in-plane orientation of the polarization field at that interface. This is a route to the formation of fluid or glassy monodomains of high polarization without the need for electric field poling. For example, unidirectional buffing of polyimide films on planar surfaces to give quadrupolar in-plane anisotropy also induces macroscopic in-plane polar order at the surfaces, enabling the formation of a variety of azimuthal polar director structures in the cell interior, including uniform and twisted states. In a π-twist cell, obtained with antiparallel, unidirectional buffing on opposing surfaces, we demonstrate three distinct modes of ferroelectric nematic electro-optic response: intrinsic, viscosity-limited, field-induced molecular reorientation; field-induced motion of domain walls separating twisted states of opposite chirality; and propagation of polarization reorientation solitons from the cell plates to the cell center upon field reversal. Chirally doped ferroelectric nematics in antiparallel-rubbed cells produce Grandjean textures of helical twist that can be unwound via field-induced polar surface reorientation transitions. Fields required are in the 3-V/mm range, indicating an in-plane polar anchoring energy of w P ∼3 × 10-3 J/m2.

Development of ferroelectric nematic fluids with giant-ε dielectricity and nonlinear optical properties.

Superhigh-ε materials that exhibit exceptionally high dielectric permittivity are recognized as potential candidates for a wide range of next-generation photonic and electronic devices. In general, achieving a high-ε state requires low material symmetry, as most known high-ε materials are symmetry-broken crystals. There are few reports on fluidic high-ε dielectrics. Here, we demonstrate how small molecules with high polarity, enabled by rational molecular design and machine learning analyses, enable the development of superhigh-ε fluid materials (dielectric permittivity, ε > 104) with strong second harmonic generation and macroscopic spontaneous polar ordering. The polar structures are confirmed to be identical for all the synthesized materials. Furthermore, adapting this strategy to high-molecular weight systems allows us to generalize this approach to polar polymeric materials, creating polar soft matters with spontaneous symmetry breaking.

Macroscopic and microscopic order parameters of lyotropic nematic liquid crystals by polarised light microscopy

ABSTRACT In this study, the birefringence (δn) and macroscopic order parameter (Q) of lyotropic nematic calamitic (NC) mesophase were obtained in the reentrant isotropic (IRE)–NC–isotropic (I) phase transition range by only examining its optical transmittance under a polarising microscope. Moreover, the microscopic order parameter (S) was found by obtaining absorption coefficients from these transmittances. Generally, the macroscopic order parameter was larger than the microscopic one. The difference between them was small near the IRE–NC phase transition and the maximum birefringence region whereas it was relatively high near the NC–I phase transition.

Symmetry-breaking-induced tipping to aging

The competing effect of heterogeneity and symmetry breaking coupling on the emerging dynamics in a system of N globally coupled Stuart-Landau oscillators is investigated. Increasing the heterogeneity, using the standard deviation of the Hopf bifurcation parameter, favors the macroscopic oscillatory state for low values of the symmetry breaking coupling and inhomogeneous steady state for larger values of the coupling. There is also a transition, tipping, to homogeneous steady state (aging state) from the macroscopic oscillatory state. The limiting factor in the diffusive coupling favors the macroscopic oscillatory state even in the presence of a large fraction of inactive oscillators in the network thereby increasing the robustness of the network. The globally coupled oscillators are reduced to a system of two evolution equations for the macroscopic order parameters, corresponding to the mean-field and the shape parameter, using the self-consistent field approach. The bifurcation diagrams obtained from the mean-field variables elucidate various bifurcation scenarios responsible for the dynamical transitions observed in N globally coupled Stuart-Landau oscillators. In particular, tipping to the aging state is found to occur via the Hopf and pitchfork bifurcations illustrating the phenomenon of bifurcation induced tipping. Analytical stability (critical) curves of these bifurcations, deduced from the mean-field variables, are found to fairly well agree with the simulation results.

Determination of order parameter and birefringence depending on temperature of nematic calamitic mesophase formed by TTAB + water binary system using polarized microscopy

In the present study, the temperature-dependent optical transmittances of lyotropic nematic calamitic mesophase formed by TTAB-water binary system were measured for certain wavelengths under polarized microscopy to obtain macroscopic order parameter with birefringence. Because birefringence in lyotropics is quite small (order of 10-3), it is very difficult to make sensitive measurements of birefringence and to obtain order parameter. The study easily achieved the order parameter depending on temperature for different wavelengths only using polarized microscopy. Therefore, the parameter could be more easily determined in liquid crystal application and the physical properties of liquid crystals, especially for lyotropics, can be better understood.