Two-Photon Spectroscopy Between States of Opposite Parities

Magnetic- and electric-dipole two-photon absorption (MED-TPA), recently introduced as a new spectroscopic technique for studying transitions between states of opposite parities, is investigated from a theoretical point of view. A new approximation, referred to as {\it weak quasi-closure approximation}, is used together with symmetry adaptation techniques to calculate the transition amplitude between states having well-defined symmetry properties. Selection rules for MED-TPA are derived and compared to selection rules for parity-forbidden electric-dipole two-photon absorption (ED-TPA).Comment: 7 pages, Revtex File, to be published in Physical Review

Anomalous small-angle X-ray scattering from charged soft matter

A review of recent applications of Anomalous Small-Angle X-ray Scattering (ASAXS) to charged soft matter systems is presented. Although the potential of ASAXS was realized in the eighties [1], applications to soft matter systems became feasible in recent years thanks to the technical developments at the synchrotron sources. Examples include both stiff chain and flexible polyelectrolytes, colloidal brush-like polyelectrolytes, DNA, RNA, and polysaccharides where the counterion profile could be determined with high precision and compared with theoretical models. In addition, ASAXS has also been found useful for microstructure characterization in soft materials. Finally, the present capability for ASAXS studies is illustrated by an example involving a surfactant micellar system

Competing interactions in arrested states of colloidal clays

Using experiments, theory and simulations, we show that the arrested state observed in a colloidal clay at intermediate concentrations is stabilized by the screened Coulomb repulsion (Wigner glass). Dilution experiments allow us to distinguish this high-concentration disconnected state, which melts upon addition of water, from a low-concentration gel state, which does not melt. Theoretical modelling and simulations reproduce the measured Small Angle X-Ray Scattering static structure factors and confirm the long-range electrostatic nature of the arrested structure. These findings are attributed to the different timescales controlling the competing attractive and repulsive interactions.Comment: Accepted for publication in Physical Review Letter

Drying dip-coated colloidal films

We present the results from a small-angle X-ray scattering (SAXS) study of lateral drying in thin films. The films, initially 10 μm thick, are cast by dip-coating a mica sheet in an aqueous silica dispersion (particle radius 8 nm, volume fraction ϕs = 0.14). During evaporation, a drying front sweeps across the film. An X-ray beam is focused on a selected spot of the film, and SAXS patterns are recorded at regular time intervals. As the film evaporates, SAXS spectra measure the ordering of particles, their volume fraction, the film thickness, and the water content, and a video camera images the solid regions of the film, recognized through their scattering of light. We find that the colloidal dispersion is first concentrated to ϕs = 0.3, where the silica particles begin to jam under the effect of their repulsive interactions. Then the particles aggregate until they form a cohesive wet solid at ϕs = 0.68 ± 0.02. Further evaporation from the wet solid leads to evacuation of water from pores of the film but leaves a residual water fraction ϕw = 0.16. The whole drying process is completed within 3 min. An important finding is that, in any spot (away from boundaries), the number of particles is conserved throughout this drying process, leading to the formation of a homogeneous deposit. This implies that no flow of particles occurs in our films during drying, a behavior distinct to that encountered in the iconic coffee-stain drying. It is argued that this type of evolution is associated with the formation of a transition region that propagates ahead of the drying front. In this region the gradient of osmotic pressure balances the drag force exerted on the particles by capillary flow toward the liquid–solid front

Arrested state of clay-water suspensions: gel or glass?

The aging of a charged colloidal system has been studied by Small Angle X-rays Scattering, in the exchanged momentum range Q=0.03 - 5 nm-1, and by Dynamic Light Scattering, at different clay concentrations (Cw =0.6 % - 2.8 %). The static structure factor, S(Q), has been determined as a function of both aging time and concentration. This is the first direct experimental evidence of the existence and evolution with aging time of two different arrested states in a single system simply obtained only by changing its volume fraction: an inhomogeneous state is reached at low concentrations, while a homogenous one is found at high concentrations.Comment: 5 pages, 2 figure

Sum Rules for Multi-Photon Spectroscopy of Ions in Finite Symmetry

Models describing one- and two-photon transitions for ions in crystalline environments are unified and extended to the case of parity-allowed and parity- forbidden p-photon transitions. The number of independent parameters for characterizing the polarization dependence is shown to depend on an ensemble of properties and rules which combine symmetry considerations and physical models.Comment: 16 pages, Tex fil

Hiding in Plain View: Colloidal Self-Assembly from Polydisperse Populations

We report small-angle x-ray scattering experiments on aqueous dispersions of colloidal silica with a broad monomodal size distribution (polydispersity, 14%; size, 8 nm). Over a range of volume fractions, the silica particles segregate to build first one, then two distinct sets of colloidal crystals. These dispersions thus demonstrate fractional crystallization and multiple-phase (bcc, Laves AB2, liquid) coexistence. Their remarkable ability to build complex crystal structures from a polydisperse population originates from the intermediate-range nature of interparticle forces, and it suggests routes for designing self-assembling colloidal crystals from the bottom up

Packing polydisperse colloids into crystals: when charge-dispersity matters

Monte Carlo simulations, fully constrained by experimental parameters, are found to agree well with a measured phase diagram of aqueous dispersions of nanoparticles with a moderate size polydispersity over a broad range of salt concentrations and volume fractions. Upon increasing volume fraction the colloids freeze first into coexisting compact solids then into a body centered cubic phase (bcc) before they melt into a glass forming liquid. The surprising stability of the bcc solid at high volume fractions and salt concentrations is explained by the interaction (charge) polydispersity and vibrational entropy

Gradients of orientation, composition and hydration of proteins for efficient light collection by the cornea of the horseshoe crab

The lateral eyes of the horseshoe crab, Limulus polyphemus, are the largest compound eyes within recent Arthropoda. While this visual system has been extensively described before, the precise mechanism allowing vision has remained controversial. Correlating quantitative refractive index (RI) mapping and detailed structural analysis, we demonstrate how gradients of RI in the cornea result from the hierarchical organization of chitin-protein fibers, heterogeneity in protein composition and bromine doping, as well as spatial variation in water content. Combining the realistic cornea structure and measured RI gradients with full-wave optical modelling and ray-tracing approaches, we show that the light collection mechanism depends on both refraction-based graded index (GRIN) optics and total internal reflection. The optical properties of the cornea are governed by different mechanisms at different hierarchical levels, demonstrating the remarkable versatility of arthropod cuticle.One-sentence summary Structural hierarchy and protein hydration determine the optical performance of the cornea of L. polyphemus.Competing Interest StatementTS and MAKAR are employed by TELIGHT. All other authors declare that they have no competing interests