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At least 343 records · Page 19

Effects of interaction strength of associating groups on linear and star polymer dynamics

A small number of associating groups incorporated onto a polymer backbone have dramatic effects on the mobility and viscoelastic response of the macromolecules in melts. These associating groups assemble, driving the formation of clusters, whose lifetime affects the properties of the polymers. In this study, we probe the effects of the interaction strength on the structure and dynamics of two topologies, linear and star polymer melts, and further investigate blends of associative and non-associating polymers using molecular dynamics simulations. Polymer chains of approximately one entanglement length are described by a bead–spring model, and the associating groups are incorporated in the form of interacting beads with an interaction strength between them that is varied from 1 to 20 k B T. We find that, for all melts and blends, interaction of a few k B T between the associating groups drives cluster formation, where the size of the clusters increases with increasing interaction strength. These clusters act as physical crosslinkers, which slow the chain mobility. Blends of chains with and without associating groups macroscopically phase separate for interaction strength between the associating groups of a few k B T and above. For weakly interacting associating groups, the static structure function S(q) is well fit by functional form predicted by the random phase approximation where a clear deviation occurs as phase segregation takes place, providing a quantitative assessment of phase segregation.

36 MATERIALS SCIENCE↗

Nonadditive Interactions Unlock Small-Particle Mobility in Binary Colloidal Monolayers

We examine the organization and dynamics of binary colloidal monolayers composed of micron-scale silica particles interspersed with smaller-diameter silica particles that serve as minority component impurities. These binary monolayers are prepared at the surface of ionic liquid droplets over a range of size ratios (σ = 0.16–0.66) and are studied with low-dose minimally perturbative scanning electron microscopy (SEM). The high resolution of SEM imaging provides direct tracking of all particle coordinates over time, enabling a complete description of the microscopic state. In these bidisperse size mixtures, particle interactions are nonadditive because interfacial pinning to the droplet surface causes the equators of differently sized particles to lie in separate planes. By varying the size ratio, we control the extent of nonadditivity in order to achieve phase behavior inaccessible to additive 2D systems. Across the range of size ratios, we tune the system from a mobile small-particle phase (σ < 0.24) to an interstitial solid (0.24 < σ < 0.33) and furthermore to a disordered glass (σ > 0.33). These distinct phase regimes are classified through measurements of hexagonal ordering of the large-particle host lattice and the lattice’s capacity for small-particle transport. Altogether, we explain these structural and dynamic trends by considering the combined influence of interparticle interactions and the colloidal packing geometry. Our measurements are reproduced in molecular dynamics simulations of 2D nonadditive disks, suggesting an efficient method for describing confined systems with reduced dimensionality representations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion Pairing Mediates Molecular Organization Across Liquid/Liquid Interfaces

Liquid/liquid interfaces play a central role in scientific fields ranging from nanomaterial synthesis and soft matter electronics to nuclear waste remediation and chemical separations. This diversity of functions arises from an interface’s ability to respond to changing conditions in its neighboring bulk phases. Understanding what drives this interfacial flexibility can provide novel avenues for designing new functional interfaces. However, limiting this progress is an inadequate understanding of the subtle intermolecular and interphase interactions taking place at the molecular level. Here, we use surface-specific vibrational sum frequency generation spectroscopy combined with atomistic molecular dynamics simulations to investigate the self-assembly and structure of model ionic oligomers consisting of an oligodimethylsiloxane (ODMS) tail covalently attached to a positively charged methyl imidazolium (MIM + ) head group at buried oil/aqueous interfaces. We show how the presence of seemingly innocuous salts can impart dramatic changes to the ODMS tail conformations in the oil phase via specific ion effects and ion-pairing interactions taking place in the aqueous phase. These specific ion interactions are shown to drive enhanced amphiphile adsorption, induce morphological changes, and disrupt emergent hydrogen-bonding structures at the interface. Tuning these interactions allows for independent control over the oligomer structure in the oil phase versus interfacial population changes and represents key mechanistic insight that is needed to control chemical reactions at liquid/liquid interfaces.

36 MATERIALS SCIENCE↗

Collective behavior of “flexicles”

In recent years the functionality of synthetic active microparticles has edged even closer to that of their biological counterparts. However, we still lack the understanding needed to recreate at the microscale key features of autonomous behavior exhibited by microorganisms or swarms of macroscopic robots. In this study, we propose a model for a three-dimensional deformable cellular composite particle consisting of self-propelled rod-shaped colloids confined within a flexible vesicle—representing a superstructure we call a “flexicle” that couples particle deformation to the internal dynamics of the internal active components. Using molecular dynamics simulations, we investigate the collective behavior of dense systems composed of many flexicles. We show that individual flexicles exhibit shape changes upon collisions with other flexicles that lead to rearrangements of the internal active rods, which slows flexicle motion. This shape deformability gives rise to a diverse set of motility-induced phase separation phenomena and the spontaneous flow of flexicles reminiscent of the migration of cells in dense tissues. Our findings establish a foundation for designing responsive, cell-like active particles and developing strategies for controlling swarm migration and other autonomous swarm behaviors at cellular and colloidal scales.

Science & Technology - Other Topics↗

Changes in nitrate binding with lanthanides in BLPhen complexes

Preorganized ligands such as bis-lactam-1,10-phenanthroline (BLPhen) offer unique selectivity trends in solvent extraction of rare-earth ions, particularly from aqueous nitrate solutions. However, due to the ligand’s lipophilicity it is experimentally challenging to obtain crystal structures of the corresponding lanthanide (Ln):ligand complexes to describe the local structure of the first coordination shell and the role of the nitrate ions in the organic phase. In this work, we report first principles molecular dynamics (FPMD) simulations of the complexation of trivalent lanthanide ions (La, Nd, and Eu) with the BLPhen ligand in the presence of nitrate ions in the dichloroethane (DCE) solvent. We find that two nitrate anions are present in the first solvation shell and the third nitrate anion is far from the first solvation shell in all three [Ln(BLPhen) 2 ] 3+ complexes examined. Moving along the lanthanide series from La to Nd to Eu, the binding pocket formed by the two BLPhen ligands shrinks in size; as a result, the two nitrate configuration changes from one-monodentate/one-bidentate binding mode for La and Nd to all monodentate for Eu. Meanwhile, the total coordination number drops from 11 for La and Nd to 10 for Eu. More interestingly, the bidentate binding in [La(BLPhen) 2 ] 3+ and [Nd(BLPhen) 2 ] 3+ complexes is highly dynamic, frequently switching to monodentate and back. The FPMD insights into the differing modes and dynamics of nitrates in the first coordination shell will be useful for further atomistic understanding of the complex structure, formation, and stability in the organic phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamics of CMEs in the LASCO Field of View

A large set (16000) of coronal mass ejections (CMEs) observed during 1996-2011 was selected to study their dynamics in the LASCO field of view (LFOV). These events were selected based on the criterion that at least three height-time measurements were available for each CME. The height-time measurements included in the SOHO/LASCO catalog were used to determine velocities and accelerations of the respective CMEs at successive distances from the Sun. Next, these parameters were sorted into 30 subsamples depending on the distance from the Sun at which they were determined. The mean velocities and accelerations calculated for the successive distance-dependent subsamples of CMEs were used to study their dynamics. We demonstrate that CMEs in the LFOV manifest three distinct phases of propagation: (i) The propelling Lorentz force dominates the dynamics of CMEs in the inner (C2 LASCO) FOV, (ii) a stable propagation occurs as a result of the balance between the propelling and drag forces, (iii) the drag force dominates at the outer edge of the LFOV. When we considered different categories of CME separately, we found different acceleration distance profiles for different categories.

Michalek, G.↗

Wake Vortex Effects Between Urban Air Mobility Aircraft

This study models the wake-induced downwash of an Urban Air Mobility (UAM) aircraft and the wake’s effects on a trailing aircraft’s dynamic stability when intersecting the wake trail. The Proctor wake vortex model is used to compute the wake-induced downwash over a 0.8 × 0.8 nautical mile flight area. The model is complemented by core radius growth, Proctor single phase wake decay, wake propagation, and Lamb wake aging. The wake data is then stored and loaded to the trailing aircraft as an atmospheric condition to affect the dynamics. Preliminary simulations include modeling the downwash from multiple UAM aircraft over the flight area and determining the normalized wake reduction at the ICAO 5 nautical mile separation criteria for a LIGHT aircraft trailing a MEDIUM aircraft.

Wake Vortex↗

Multibody Simulation of REMORA CubeSat Docking to and Pushing a Spent Rocket Booster

This paper details the multibody simulation of three phases of critical importance to the feasibility of the REMORA CubeSat space debris mitigation concept: the final approach of the CubeSat to a spent rocket booster; the grappling of the spent rocket booster using a robotic arm; and the pushing of the spent rocket booster to divert its course from another on-orbit asset. The extension of a robotic mobility and manipulation modeling toolkit (M3TK) from multibody dynamics simulation of manipulators and ground vehicles to simulation of orbital robotics is outlined. This includes the identification of the appropriate parameters required to concisely and generically describe thruster loads, thruster mixing, spacecraft control, and spacecraft navigation for the purpose of on-orbit robotics simulation. A high-level spacecraft navigator commands maneuvers to target spacecraft states. A PID spacecraft controller takes the target states and calculates desired forces and torques. A thruster mixer solves a quadratic program to determine the optimal thruster firing times for the propulsion system. Pulse width modulated actuation of eight canted cold gas thrusters is used in the simulated approach to a rocket nozzle from a distance of 200 m. A five degree of freedom robotic arm is controlled to position a pair of pincers to grasp the rocket nozzle. Contact dynamics are used to accurately simulate the grasping of the rocket nozzle by the pincers. A similar, but separate simulation is performed to assess the ability of the REMORA CubeSat to push the large spent rocket booster. This diversion maneuver makes use of an additional, larger thruster, and pushes the rocket booster in excess of 400 m. Appropriate motor control gains on the robotic arm are found to be higher during the pushing phase than those which are appropriate during free motion; this increase promotes rigidity of the arm and allows it to properly direct the pushing force. Challenges encountered in time step selection for numerical stability of the simulation are also discussed.

Mukherjee, Rudranarayan↗

Elucidating the speciation of extracted lanthanides by diglycolamides

Many studies over the past few decades have been devoted to addressing the application of diglycolamides (DGAs) for hydrometallurgical-based, f-element separations. Work to date has shown the molecular structure of a DGA derivative can have a significant impact on intra-lanthanide partitioning patterns. More recent studies have pushed towards probing the structure function relationship of the lanthanide-DGA complex to enable the design of more efficient lanthanide separation systems. Spectroscopic techniques, such as UV–Visible, Fourier Transformed Infrared Spectroscopy (FT-IR), Nuclear Magnetic Resonance (NMR), and Extended X-ray Absorption Fine Structure (EXAFS), provide information regarding the inner-sphere coordination of a given lanthanide-DGA complex. Scattering techniques, such as Dynamic Light Scattering (DLS), Small-Angle X-ray Scattering (SAXS), and Small-Angle Neutron Scattering (SANS), address nanoscale structures including aggregate sizes and morphology. Here, this review assesses the current state-of-knowledge regarding lanthanide-DGA hydrometallurgical (i.e., solvent extraction systems) interrogated using spectroscopic and scattering techniques to characterize the extracted Ln 3+ DGA species. Of particular interest to this review is the impact of varied diluents, inclusion and variation of phase modifiers, and DGA derivatization on system characteristics. While there has been extensive literature on the application of DGAs for f-element separations, the literature lacks a collective assessment of the speciation of Ln 3+ in the organic phase. This review provides new insights into the field of DGA separations, explicitly with an application to intra-lanthanide separations. Specifically, this review illustrates the importance of both the co-extraction anion (Cl - , NO 3 - , or ClO 4 - ) as it pertains to both the aggregate size and Ln 3+ distribution coefficient. It is evident the ability of the anion to disrupt the hydrogen bonding network limits both aggregate size and distribution coefficients according to the Hoffmeister series. This suggests the importance of the large, softer anions with a low charge-to-surface area ratio on encouraging hydrogen bond interactions. In addition, the co-extracted cation (H + vs Na + ) is important for mitigating transfer of Ln 3+ from the aqueous to the organic phase through extensive hydrogen bonding networks. These networks are responsible for forming supramolecular aggregates where a change in morphology is observed with increasing concentrations of H + and/or Ln 3+ in the organic phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thiocyanate Ions Form Antiparallel Populations at the Concentrated Electrolyte/Charged Surfactant Interface

Anions play significant roles in the separation of lanthanides and actinides. The molecular-scale details of how these anions behave at aqueous interfaces are not well understood, especially at high ionic strengths. Here, we describe the interfacial structure of thiocyanate anions at a soft charged interface up to 5 M bulk concentration with combined classical and phase-sensitive and molecular dynamics (MD) simulations. At low concentrations thiocyanate ions are mostly oriented with their sulfur end pointing toward the charged surfactants. In this work, the VSFG signal reaches a plateau at around 100 mM bulk concentration, followed by significant changes above 1 M. At high concentrations a new thiocyanate population emerges with their sulfur end pointing toward the bulk liquid. The –CN stretch frequency is different for up and down oriented SCN – ions, indicating different coordination environments. These results provide key molecular-level insights for the interfacial behavior of complex anions in highly concentrated solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Results From the Physics of Colloids Experiment on ISS

The Physics of Colloids in Space (PCS) experiment was accommodated within International Space Station (ISS) EXpedite the PRocessing of Experiments to Space Station (EXPRESS) Rack 2 and was remotely operated from early June 2001 until February 2002 from NASA Glenn Research Center's Telescience Support Center (TSC) in Cleveland, Ohio, and from the remote site at Harvard University in Cambridge, Massachusetts. PCS was launched on 4/19/2001 on Space Shuttle STS-100. The experiment was activated on 5/31/2001. The entire experimental setup performed remarkably well, and accomplished 2400 hours of science operations on-orbit. The sophisticated instrumentation in PCS is capable of dynamic and static light scattering from 11 to 169 degrees, Bragg scattering over the range from 10 to 60 degrees, dynamic and static light scattering at low angles from 0.3 to 6.0 degrees, and color imaging. The long duration microgravity environment on the ISS facilitated extended studies on the growth and coarsening characteristics of binary crystals. The de-mixing of the colloid-polymer critical-point sample was also studied as it phase-separated into two phases. Further, aging studies on a col-pol gel, gelation rate studies in extremely low concentration fractal gels over several days, and studies on a glass sample, all provided valuable information. Several exciting and unique aspects of these results are discussed here.

Weitz, David↗

Low-dimensional description of the dynamics in separated flow past thick airfoils

Results are presented for the numerical simulation of unsteady viscous incompressible flow past thick airfoils. Specifically, flow past a NACA 4424 at an angle of attack of 2.5 deg and Reynolds numbers in the range of 1700-4000 has been simulated using the spectral element method. At these conditions the flow is separatedd and an unsteady wake is formed. Application of the method of empirical eigenfunction reveals the structure of the most energetic components of the flow. These are found to occur in pairs that, through phase exchange, are responsible for the vortex shedding. A set of ordinary differential equations is obtained for the amplitudes of these eigenfunctions by a Galerkin projection of the Navier-Stokes equations. The solutions of the model system are compared with the full simulation. The work is of relevance to the transition process and observed routes to chaos in airfoil wakes.

Deane, Anil E.↗

Photoinduced structural recovery dynamics of rare-earth nickelate thin films

Photoinduced structural dynamics of rare-earth nickelate thin films, NdNiO 3 and SmNiO 3 , grown on (001) oriented SrTiO 3 were studied using time-resolved x-ray diffraction. The evolution of the (002) Bragg peak was tracked following laser excitation. The recovery pathways were found to be strongly dependent on laser fluence for NdNiO 3 and distinct for the two rare-earth nickelates. The recovery of the (002) peak shifts was modeled using a one-dimensional thermal diffusion model which showed that the recovery processes are non-thermal at high fluences. For NdNiO 3 , the timescales for the recovery of the (002) peak shift were found to be closely related to Ni magnetism recovery, potentially indicating magneto-structural coupling. Moreover, the evolution of integrated intensity and full-width-half-maximum points towards the presence of a structural phase separation during recovery. In conclusion, our studies highlight structural recovery pathways in nickelates by comparing the distinct responses of the photoinduced metal-insulator transition in NdNiO 3 and SmNiO 3 .

36 MATERIALS SCIENCE↗

Geometric decoherence time in Lindbladian dynamics

The onset of decoherence in open many-body systems lacks a dynamical timescale grounded in the loss of bipartite entanglement. Here, we introduce the geometric decoherence time, defined as the earliest moment the monotone relation between logarithmic negativity and Rényi-$\frac{1}{2}$ entropy—exactly equal across any bipartition for pure states—breaks down under open-system evolution, signaling entropy growth without accompanying entanglement growth. We establish this criterion in both single-particle Gaussian dynamics and many-body Lindbladian evolution. We show that quantum mutual information provides a complementary long-time diagnostic: Its asymptotic vanishing is equivalent to factorization of the steady state across the bipartition, a condition strictly stronger than separability, and whenever a product steady state is approached exponentially in trace norm, negativity and mutual information share the same decay rate. In the presence of a strong symmetry, this tracking can fail—residual classical correlations can survive after entanglement has vanished. In the Kitaev chain with balanced gain and loss, we derive a closed-form solution and show that the topological phase sustains longer coherence times than the trivial phase at identical dissipation, with a local minimum at the chiral-symmetric point. In the interacting XXZ chain, exact many-body evolution shows that local 𝑍 dephasing preserves residual classical correlations, whereas gain and loss restore the mutual-information tracking of negativity. Furthermore, our results establish the geometric decoherence time as a dynamical scale tracking the onset of decoherence.

74 ATOMIC AND MOLECULAR PHYSICS↗

Unexpected Kinetic Solvent Effects Enhance Activity and Selectivity in Biphasic Systems

Biphasic dehydration of fructose to 5-hydroxymethylfurfural (HMF) has shown unprecedented increases in productivity, but a mechanistic understanding is lacking. Herein, we couple fast experimental reaction kinetics, multiscale modeling (phase behavior, classical molecular dynamics(MD), and quantum mechanics/molecular mechanics MD), in situ sampling, and IR and 13 C-NMR spectroscopy to elucidate the complex effects of nonpolar extracting organic solvents on the kinetics of fructose dehydration. We show that these organic solvents can reach significant mutual solubility with water at reaction temperatures, enabling the partition of the sugar and catalyst into the extracting phase. In the organic-rich environment, the dehydration of fructose proceeds faster and more selectively than in water due to increased relative abundance of the reactive furanose isomer, enhanced water–catalyst–substrate interactions driven by nanophase separation, and higher product stability stemming from preferential solvation. Furthermore, we demonstrate that these solvent effects impact other critical biphasic reactions in biomass upgrading and provide qualitative principles for solvent selection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning nonequilibrium phase transitions with inertia

In striking contrast to equilibrium systems, inertia can profoundly alter the structure of active systems. Here, we demonstrate that driven systems can exhibit effective equilibrium-like states with increasing particle inertia, despite rigorously violating the fluctuation–dissipation theorem. Increasing inertia progressively eliminates motility-induced phase separation and restores equilibrium crystallization for active Brownian spheres. This effect appears to be general for a wide class of active systems, including those driven by deterministic time-dependent external fields, whose nonequilibrium patterns ultimately disappear with increasing inertia. The path to this effective equilibrium limit can be complex, with finite inertia sometimes acting to accentuate nonequilibrium transitions. The restoration of near equilibrium statistics can be understood through the conversion of active momentum sources to passive-like stresses. Unlike truly equilibrium systems, the effective temperature is now density dependent, the only remnant of the nonequilibrium dynamics. Further, this density-dependent temperature can in principle introduce departures from equilibrium expectations, particularly in response to strong gradients. Our results provide additional insight into the effective temperature ansatz while revealing a mechanism to tune nonequilibrium phase transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Twist Angle-Dependent Interlayer Exciton Lifetimes in van der Waals Heterostructures

In van der Waals (vdW) heterostructures formed by stacking two monolayers of transition metal dichalcogenides, multiple exciton resonances with highly tunable properties are formed and subject to both vertical and lateral confinement. We investigate how a unique control knob, the twist angle between the two monolayers, can be used to control the exciton dynamics. We observe that the interlayer exciton lifetimes in MoSe 2 /WSe 2 twisted bilayers (TBLs) change by one order of magnitude when the twist angle is varied from 1° to 3.5°. Additionally, using a low-energy continuum model, we theoretically separate two leading mechanisms that influence interlayer exciton radiative lifetimes. The shift to indirect transitions in the momentum space with an increasing twist angle and the energy modulation from the moiré potential both have a significant impact on interlayer exciton lifetimes. We further predict distinct temperature dependence of interlayer exciton lifetimes in TBLs with different twist angles, which is partially validated by experiments. While many recent studies have highlighted how the twist angle in a vdW TBL can be used to engineer the ground states and quantum phases due to many-body interaction, our studies explore its role in controlling the dynamics of optically excited states, thus, expanding the conceptual applications of “twistronics”.

36 MATERIALS SCIENCE↗

Dielectron production in central Pb-Pb collisions at $\sqrt{s_{NN}}$ = 5.02TeV

The first measurement of the 𝑒 + ⁢𝑒 − pair production at midrapidity and low invariant mass in central Pb-Pb collisions at $\sqrt{s_{NN}}$ = 5.02 TeV at the Large Hadron Collider is presented. The yield of 𝑒 + ⁢𝑒 − pairs is compared with a cocktail of expected hadronic decay contributions in the invariant mass (𝑚𝑒⁢𝑒) and pair transverse momentum (𝑝 T,𝑒⁢𝑒 ) ranges 𝑚 𝑒⁢𝑒 < 3.5 GeV/𝑐 2 and 𝑝 T,𝑒⁢𝑒 < 8 GeV/𝑐. For 0.18 < 𝑚 𝑒⁢𝑒 < 0.5 GeV/𝑐 2 the ratio of data to the cocktail of hadronic contributions amounts to 1.40 ± 0.11⁢(stat.) ± 0.23 ⁢(syst.) ± 0.16⁢ (cocktail) and 1.42 ± 0.11⁢ (stat.) ± 0.23 (syst.)$^{+0.24}_{−0.29}$ ⁢(cocktail), including or not including medium effects in the estimation of the heavy-flavor background, respectively. It is consistent with predictions from two different models for an additional contribution of thermal 𝑒+⁢𝑒− pairs from the hadronic and partonic phases. In the intermediate-mass range (1.2 < 𝑚 𝑒⁢𝑒 < 2.6 GeV/𝑐 2 ), the pair transverse impact parameter of the 𝑒 + ⁢𝑒 − pairs (DCA𝑒⁢𝑒, where “DCA” denotes “distance of closest approach”) is used for the first time in Pb-Pb collisions to separate displaced dielectrons from heavy-flavor hadron decays from a possible (thermal) contribution produced at the interaction point. The data are consistent with a suppression of 𝑒 + ⁢𝑒 − pairs from $𝑐\bar{𝑐}$ and an additional prompt component. Finally, the first direct-photon measurement in the 10% most central Pb-Pb collisions at $\sqrt{s_{NN}}$ = 5.02 TeV is reported via the study of virtual direct photons in the transverse momentum range 1 < 𝑝 T < 5 GeV/𝑐. A model including prompt photons, as well as photons from the preequilibrium and fluid-dynamic phases, can reproduce the result, while being at the upper edge of the data uncertainties.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗