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In dense systems of hard-interacting colloidal particles with anisotropic shapes, crystallization pathways represent an interesting frontier since directional entropic forces often cause fascinating variations in the equilibrium crystal structures. At increasing densities, when the orientational excluded volumes of anisotropic particles start overlapping, their translational and rotational dynamics become coupled, introducing complexities in the kinetics of their configurational reorganization, which facilitates ordering. To elucidate this, we have studied a two-dimensional system of osmotically compressed corner-rounded Brownian square platelets, which are known to equilibrate into hexagonal and rhombic crystalline phases as the osmotic pressure is increased. By analyzing the translational and orientational dynamics of the particles and calculating their corresponding contributions to minimize the free energy, we have shown that the accessible range of orientational diffusion of particles governs the pathways of structural evolution and consequent optimal equilibrium ordering at a given osmotic pressure. As the accessible orientational excursion becomes wider, the rotational contribution to configurational entropy minimizes the total free energy, leading to hexagonal ordering. At higher osmotic pressures, the long collective translational fluctuations of side-aligned particles with restricted rotational diffusion maximize entropy, thereby inducing a free energetically favored rhombic crystalline structure. Intriguingly, the density, which solely governs the crystallization of hard spheres, does not have any direct effect on this process. Complementary Brownian dynamics simulations further corroborate these experimental observations and interpretations. Our findings are also relevant to other systems of hard interacting anisotropic shapes in two and three dimensions., Comment: 8 pages, 4 figures and Supplementary Information

Polymer microgels exhibit intriguing macroscopic flow properties arising from their unique microscopic structure. Microgel colloids comprise a crosslinked polymer network with a radially decaying density profile, resulting in a dense core surrounded by a fuzzy corona. Notably, microgels synthesized from poly(N-isopropylacrylamide) (PNIPAM) are thermoresponsive, capable of adjusting their size and density profile based on temperature. Above the lower critical solution temperature ($T_\text{LCST}\sim 33$ $^\circ$C), the microgel's polymer network collapses, leading to the expulsion of water through a reversible process. Conversely, below $33$ $^\circ$C, the microgel's network swells, becoming highly compressible and allowing overpacking to effective volume fractions exceeding one. Under conditions of dense packing, microgels undergo deformation in distinct stages: corona compression and faceting, interpenetration, and finally, isotropic compression. Each stage exhibits a characteristic signature in the yield stress and elastic modulus of the dense microgel suspensions. Here, we introduce a model for the linear elastic shear modulus through the minimization of a quasi-equilibrium free energy, encompassing all relevant energetic contributions. We validate our model by comparing its predictions to experimental results from oscillatory shear rheology tests on microgel suspensions at different densities and temperatures. Our findings demonstrate that combining macroscopic rheological measurements with the model allows for temperature-dependent characterization of polymer interaction parameters., Comment: 23 pages, 4 figures; We have corrected the polymer concentrations; they should be given in wt % instead of g/ml

The coadjoint orbits of compact Lie groups each carry a canonical (positive definite) K\"ahler structure, famously used to realize the group's irreducible representations in holomorphic sections of appropriate line bundles (Borel-Weil theorem). Less studied are the (indefinite) invariant *pseudo*-K\"ahler structures they also admit, which can be used to realize the same representations in higher cohomology of the sections (Bott's theorem). Using ``eigenflag'' embeddings, we give a very explicit description of these metrics in the case of the unitary group. As a byproduct we show that $U_n/(U_{n_1}\times\cdots\times U_{n_k})$ has exactly $k!$ invariant complex structures, a count which seems to have hitherto escaped attention., Comment: 20 pages, 2 figures. Accepted version, to appear in Differential Geometry and its Applications

We investigate the translational and rotational relaxation dynamics of a crowded two-dimensional system of monodisperse Penrose kites, in which crystallization, quasi-crystallization, and nematic ordering are suppressed, from low to high area fractions along the metastable ergodic fluid branch. First, we demonstrate a decoupling between both the translational and the rotational diffusion coefficients and the relaxation time: the diffusivities are not inversely proportional to the relaxation time, neither in the low-density normal liquid regime nor in the high-density supercooled regime. Our simulations reveal that this inverse proportionality breaks in the normal liquid regime due to the Mermin-Wagner long-wavelength fluctuations and in the supercooled regime due to the dynamical heterogeneities. We then show that dynamical heterogeneities are mainly spatial for translational degrees of freedom and temporal for rotational ones, that there is no correlation between the particles with the largest translational and rotational displacements, and that different dynamical length scales characterize the translational and the rotational motion. Hence, despite the translational and the rotational glass-transition densities coincide, according to a mode-coupling fit, translations and rotations appear to decorrelate via different dynamical processes., Comment: Physical Review Material, to appear

Long-wavelength Mermin-Wagner fluctuations prevent the existence of translational long-range order, in two-dimensional systems at finite temperature. Their dynamical signature, which is the divergence of the vibrational amplitude with the system size, also affects disordered solids and washes out the transient solid-like response generally exhibited by liquids cooled below their melting temperature. Through a combined numerical and experimental investigation, here we show that long-wavelength fluctuations are also relevant at high temperature, where the liquid dynamics does not reveal a transient solid-like response. In this regime, they induce an unusual but ubiquitous decoupling between long-time diffusion coefficient $D$ and structural relaxation time $\tau$, where $D\propto \tau^{-\kappa}$, with $\kappa > 1$. Long-wavelength fluctuations have a negligible influence on the relaxation dynamics only at extremely high temperatures, in molecular liquids, or extremely low densities, in colloidal systems.

We investigate structural and dynamical properties of moderately polydisperse emulsions across an extended range of droplet volume fractions phgr, encompassing fluid and glassy states up to jamming. Combining experiments and simulations, we show that when $\phi$ approaches the glass transition volume fraction ${{\phi}_{g}}$ , dynamical heterogeneities and amorphous order arise within the emulsion. In particular, we find an increasing number of clusters of particles having five-fold symmetry (i.e. the so-called locally favoured structures, LFS) as $\phi$ approaches ${{\phi}_{g}}$ , saturating to a roughly constant value in the glassy regime. However, contrary to previous studies, we do not observe a corresponding growth of medium-range crystalline order; instead, the emergence of LFS is decoupled from the appearance of more ordered regions in our system. We also find that the static correlation lengths associated with the LFS and with the fastest particles can be successfully related to the relaxation time of the system. By contrast, this does not hold for the length associated with the orientational order. Our study reveals the existence of a link between dynamics and structure close to the glass transition even in the absence of crystalline precursors or crystallization. Furthermore, the quantitative agreement between our confocal microscopy experiments and Brownian dynamics simulations indicates that emulsions are and will continue to be important model systems for the investigation of the glass transition and beyond., Comment: J. Stat. Mech. (2016) 094003 --- special issue of JSTAT "The Role of Structure in Glassy and Jammed Systems "

We model the packing structure of a marginally jammed bulk ensemble of polydisperse spheres using an extended granocentric mode explicitly taking into account rattlers. This leads to a relation- ship between the characteristic parameters of the packing, such as the mean number of neighbors and the fraction of rattlers, and the radial distribution function g(r). We find excellent agreement between the model predictions for g(r) and packing simulations as well as experiments on jammed emulsion droplets. The observed quantitative agreement opens the path towards a full structural characterization of jammed particle systems for imaging and scattering experiments., Comment: submitted

Metallic conductors that are optically transparent represent a rare breed of generally contraindicated physical properties that are nevertheless critically needed for application where both functionalities are crucial. Such rare materials have traditionally been searched in the general chemical neighborhood of compounds containing metal oxides, expected to be wide gap insulators that might be doped to induce conductivity.Focusing on the family of 18 valence electron ABX compounds we have searched theoretically for the ability of the compound's electronic structure to simultaneously lead to optical transparency, in parallel with the ability of its intrinsic defect structures to produce uncompensated free holes.This led to the prediction of a stable, never before synthesized TaIrGe compound made of all-metal heavy atom compound as the "best of class" from the V-IX-IV group. Laboratory synthesis then found it to be stable in the predicted crystal structure and p-type transparent conductor with measured strong direct absorption of 3.36 eV and remarkably high (albeit not predicted) hole mobility of 2730 cm2/Vs at room temperature. This methodology opens the way to future searches of transparent conductors in unexpected chemical groups., Comment: 5 figures

Droplet microfluidics has emerged as a powerful platform allowing a large number of individual reactions to be carried out in spatially distinct microcompartments. Due to their small size, however, the spectroscopic characterisation of species encapsulated in such systems remains challenging. In this paper, we demonstrate the acquisition of infrared spectra from single microdroplets containing aggregation-prone proteins. To this effect, droplets are generated in a microfluidic flow-focussing device and subsequently deposited in a square array onto a ZnSe prism using a micro stamp. After drying, the solutes present in the droplets are illuminated locally by an infrared laser through the prism, and their thermal expansion upon absorption of infrared radiation is measured with an atomic force microscopy tip, granting nanoscale resolution. Using this approach, we resolve structural differences in the amide bands of the spectra of monomeric and aggregated lysozyme from single microdroplets with picolitre volume., Comment: 5 pages, 3 Figures

We discuss the linear and non-linear rheology of concentrated (sub)microscale emulsions, amorphous disordered solids composed of repulsive and deformable soft colloidal spheres. Based on recent results from simulation and theory, we derive quantitative predictions for the dependences of the elastic shear modulus and the yield stress on the droplet volume fraction. The remarkable agreement with experiments we observe supports the scenario that the repulsive glass and the jammed state can be clearly identified in the rheology of soft spheres at finite temperature while crossing continuously from a liquid to a highly compressed yet disordered solid., Comment: submitted

We show how attractive interactions dramatically influence emulsion rheology. Unlike the repulsive case, attractive emulsions below random close packing, RCP, can form soft gel-like elastic solids. However, above RCP, attractive and repulsive emulsions have similar elasticities. Such compressed attractive emulsions undergo an additional shear-driven relaxation process during yielding. Our results suggest that attractive emulsions begin to yield at weak points through the breakage of bonds, and, above RCP, also undergo droplet configurational rearrangements.

Ankylography is a new 3D imaging technique, which, under certain circumstances, enables reconstruction of a 3D object from a single sample orientation. Here, we provide a matrix rank analysis to explain the principle of ankylography. We then present an ankylography experiment on a microscale phase object using an optical laser. Coherent diffraction patterns are acquired from the phase object using a planar CCD detector and are projected onto a spherical shell. The 3D structure of the object is directly reconstructed from the spherical diffraction pattern. This work may potentially open the door to a new method for 3D imaging of phase objects in the visible light region. Finally, the extension of ankylography to more complicated and larger objects is suggested., Comment: 22 pages 5 figures