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At least 1,423 records · Page 79

Discovery of enhanced lattice dynamics in a single-layered hybrid perovskite

Layered hybrid perovskites exhibit emergent physical properties and exceptional functional performances, but the coexistence of lattice order and structural disorder severely hinders our understanding of these materials. One unsolved problem regards how the lattice dynamics are affected by the dimensional engineering of the inorganic frameworks and their interaction with the molecular moieties. Here, we address this question by using a combination of spontaneous Raman scattering, terahertz spectroscopy, and molecular dynamics simulations. This approach reveals the structural dynamics in and out of equilibrium and provides unexpected observables that differentiate single- and double-layered perovskites. While no distinct vibrational coherence is observed in double-layered perovskites, an off-resonant terahertz pulse can drive a long-lived coherent phonon mode in the single-layered system. This difference highlights the dramatic change in the lattice environment as the dimension is reduced, and the findings pave the way for ultrafast structural engineering and high-speed optical modulators based on layered perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vibronic coupling-driven symmetry breaking and solvation in the photoexcited dynamics of quadrupolar dyes

Quadrupolar dyes, such as acceptor–donor–acceptor molecules, are highly relevant for applications in nonlinear optics and photovoltaics. They are also versatile models for exploring photoinduced charge-transfer dynamics. The interplay between electronic and vibronic couplings in these molecules may break excited-state symmetry, resulting in intramolecular charge separation and pronounced solvatochromism. Experimentally, distinguishing the roles of intramolecular vibronic coupling and solvent reorganization for the initial charge-transfer dynamics has been challenging so far. Here we investigate a prototypical quadrupolar dye in polar and non-polar solvents using ultrafast pump–probe and two-dimensional electronic spectroscopy. Our results reveal that vibronic couplings initiate excited-state symmetry breaking during the first ~50 fs of the photoinduced charge transfer, whereas solvent-induced charge localization sets in at later times. Quantum dynamics and electronic structure simulations support our experimental findings. Our results reveal the details of solvation dynamics in photoexcited molecules and suggest strategies for their manipulation through vibronic couplings.

36 MATERIALS SCIENCE↗

Magnetic Energy Release, Plasma Dynamics, and Particle Acceleration in Relativistic Turbulent Magnetic Reconnection

In strongly magnetized astrophysical plasma systems, magnetic reconnection is believed to be the primary process during which explosive energy release and particle acceleration occur, leading to significant high-energy emission. Past years have witnessed active development of kinetic modeling of relativistic magnetic reconnection, supporting this magnetically dominated scenario. A much less explored issue in studies of relativistic reconnection is the consequence of three-dimensional dynamics, where turbulent structures are naturally generated as various types of instabilities develop. This paper presents a series of three-dimensional, fully kinetic simulations of relativistic turbulent magnetic reconnection (RTMR) in positron–electron plasmas with system domains much larger than kinetic scales. Our simulations start from a force-free current sheet with several different modes of long-wavelength magnetic field perturbations, which drive additional turbulence in the reconnection region. Because of this, the current layer breaks up and the reconnection region quickly evolves into a turbulent layer filled with coherent structures such as flux ropes and current sheets. Additionally, we find that plasma dynamics in RTMR is vastly different from its 2D counterpart in many aspects. The flux ropes evolve rapidly after their generation, and can be completely disrupted by the secondary kink instability. This turbulent evolution leads to superdiffusive behavior of magnetic field lines as seen in MHD studies of turbulent reconnection. Meanwhile, nonthermal particle acceleration and the timescale for energy release can be very fast and do not depend strongly on the turbulence amplitude. Additionally, the main acceleration mechanism is a Fermi-like acceleration process supported by the motional electric field, whereas the nonideal electric field acceleration plays a subdominant role. We also discuss possible observational implications of three-dimensional RTMR in high-energy astrophysics.

79 ASTRONOMY AND ASTROPHYSICS↗

Cryo-EM structures of Escherichia coli cytochrome bo 3 reveal bound phospholipids and ubiquinone-8 in a dynamic substrate binding site

Two independent structures of the proton-pumping, respiratory cytochrome bo3 ubiquinol oxidase (cyt bo 3 ) have been determined by cryogenic electron microscopy (cryo-EM) in styrene–maleic acid (SMA) copolymer nanodiscs and in membrane scaffold protein (MSP) nanodiscs to 2.55- and 2.19-Å resolution, respectively. The structures include the metal redox centers (heme b, heme o 3 , and Cu B ), the redox-active cross-linked histidine–tyrosine cofactor, and the internal water molecules in the proton-conducting D channel. Each structure also contains one equivalent of ubiquinone-8 (UQ8) in the substrate binding site as well as several phospholipid molecules. The isoprene side chain of UQ8 is clamped within a hydrophobic groove in subunit I by transmembrane helix TM0, which is only present in quinol oxidases and not in the closely related cytochrome c oxidases. Both structures show carbonyl O1 of the UQ8 headgroup hydrogen bonded to D75I and R71 I . In both structures, residue H98 I occupies two conformations. In conformation 1, H98 I forms a hydrogen bond with carbonyl O4 of the UQ8 headgroup, but in conformation 2, the imidazole side chain of H98 I has flipped to form a hydrogen bond with E14 I at the N-terminal end of TM0. We propose that H98 I dynamics facilitate proton transfer from ubiquinol to the periplasmic aqueous phase during oxidation of the substrate. Computational studies show that TM0 creates a channel, allowing access of water to the ubiquinol headgroup and to H98 I .

bioenergetics↗

Dynamic Implications of Noncovalent Interactions in Amphiphilic Single-Chain Polymer Nanoparticles

Single-chain polymer nanoparticles (SCNPs) combine the chemical diversity of synthetic polymers with the intricate structure of biopolymers, generating versatile biomimetic materials. The mobility of polymer chain segments at length scales similar to secondary structural elements in proteins is critical to SCNP structure and thus function. However, the influence of noncovalent interactions used to form SCNPs (e.g., hydrogen-bonding and biomimetic secondary-like structure) on these conformational dynamics is challenging to quantitatively assess. To isolate the effects of noncovalent interactions on SCNP structure and conformational dynamics, we synthesized a series of amphiphilic copolymers containing dimethylacrylamide and monomers capable of forming these different interactions: (1) di(phenylalanine) acrylamide that forms intramolecular β-sheet-like cross-links, (2) phenylalanine acrylamide that forms hydrogen-bonds but lacks a defined local structure, and (3) benzyl acrylamide that has the lowest propensity for hydrogen-bonding. Each SCNP formed folded structures comparable to those of intrinsically disordered proteins, as observed by size exclusion chromatography and small angle neutron scattering. The dynamics of these polymers, as characterized by a combination of dynamic light scattering and neutron spin echo spectroscopy, was well described using the Zimm with internal friction (ZIF) model, highlighting the role of each noncovalent interaction to additively restrict the internal relaxations of SCNPs. These results demonstrate the utility of local scale interactions to control SCNP polymer dynamics, guiding the design of functional biomimetic materials with refined binding sites and tunable kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Wind Loading on CSP Collectors Caused by Turbulent Wind Fluctuations: Insights from a 2-Year Field Campaign

Concentrating Solar Power (CSP) is a promising solar technology for electricity generation with thermal energy storage and with the additional benefit of industrial heat production. Wind loading on CSP collector structures, such as parabolic troughs or heliostats, is one of the primary drivers of their structural design costs. In particular, dynamic wind loading is a major source of uncertainty in the collector design process, which heavily relies on wind tunnel testing. In the field, the turbulent nature of the incoming wind creates fluctuating loads (support structure loads and resulting mirror deflections) on the collectors, with impacts on fatigue lifetime and optical performance. As is well known, wind tunnel tests cannot entirely reproduce the complex turbulent wind conditions typically observed at full-scale plants. To shed light on this topic, NREL initiated a field campaign at the operational Nevada Solar One (NSO) powerplant that uses parabolic troughs as solar collectors. The aim of the project is a detailed characterization of prevailing wind and turbulence conditions and resulting operational loads on parabolic troughs. We use the published 2-year dataset of high-resolution combined wind and structural loads measurements [1] to characterize the dynamic structural wind response. For quantifying dynamic wind loading, we apply the concept of admittance functions, which are spectral transfer functions that couple the turbulent wind to resulting structural loads (aerodynamic admittance), and to the structural response (mechanical admittance). In practice, aerodynamic admittance describes which turbulent eddy sizes are effective in creating structural loads. The mechanical admittance describes in which frequency ranges these loads are reinforced or dampened by the structure. While these functions are an established concept in civil engineering, their recent application to a single full-scale heliostat [2] proved their broader applicability to CSP collectors. Here, we present a characterization of admittance functions for full-scale parabolic trough collectors and show how wind characteristics (mean wind speed and direction, turbulent kinetic energy, turbulent length scales), the sun-tracking trough angle, and row position alter the admittance functions. Further, we study to which extent the admittance functions are universal for a specific trough geometry and how our findings compare to reported heliostat results. References [1] https://data.openei.org/submissions/5938. [2] Blume, K., Roger, M., and Pitz-Paal, R. 2023b. "Simplified analytical model to describe wind loads and wind-induced tracking deviations of heliostats." Solar Energy, 256, 96-109. https://doi.org/10.1016/j.solener.2023.03.055.

admittance functions↗

Static and dynamic magnetic properties of honeycomb lattice antiferromagnets Na 2 M 2 TeO 6 , M = Co and Ni

The magnetic structures and spin dynamics of Na 2 CO 2 TeO 6 and Na 2 Ni 2 TeO 6 are investigated by means of elastic and inelastic neutron scattering measurements and the results are discussed in the context of a generalized Kitaev-Heisenberg model on a honeycomb lattice with strong spin-orbit coupling. The large number of parameters involved in the Hamiltonian model is evaluated by using an iterative optimization algorithm capable of extracting model solutions and simultaneously estimating their uncertainty. The analyses indicate that both Co 2+ (d 7 ) and Ni 2+ (d 8 ) antiferromagnets realize bond-dependent anisotropic nearest-neighbor interactions and support the theoretical predictions for the realization of Kitaev physics in 3 d electron systems with effective spins S = 1/2 and 1. By studying the Na-doped system Na 2.4 Ni 2 TeO 6 , we show that the control of Na content can provide an effective route for fine-tuning the magnetic lattice dimensionality, as well as to controlling the bond-dependent anisotropic interactions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Predictive Model of Charge Mobilities in Organic Semiconductor Small Molecules with Force-Matched Potentials

Charge mobility of crystalline organic semiconductors (OSC) is limited by local dynamic disorder. Recently, the charge mobility for several high mobility OSCs, including TIPS-pentacene, were accurately predicted from a density functional theory (DFT) simulation constrained by the crystal structure and the inelastic neutron scattering spectrum, which provide direct measures of the structure and the dynamic disorder in the length scale and energy range of interest. However, the computational expense required for calculating all of the atomic and molecular forces is prohibitive. In this work, we demonstrate the use of density functional tight binding (DFTB), a semiempirical quantum mechanical method that is 2 to 3 orders of magnitude more efficient than DFT. We show that force matching a many-body interaction potential to DFT derived forces yields highly accurate DFTB models capable of reproducing the low-frequency intricacies of experimental inelastic neutron scattering (INS) spectra and accurately predicting charge mobility. We subsequently predicted charge mobilities from our DFTB model of a number of previously unstudied structural analogues to TIPS-pentacene using dynamic disorder from DFTB and transient localization theory. The approach we establish here could provide a truly rapid simulation pathway for accurate materials properties prediction, in our vision applied to new OSCs with tailored properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Sheaf Theoretical Approach to Uncertainty Quantification of Heterogeneous Geolocation Information

Integration of multiple, heterogeneous sensors is a challenging problem across a range of applications. Prominent among these are multi-target tracking, where one must combine observations from different sensor types in a meaningful and efficient way to track multiple targets. Because different sensors have differing error models, we seek a theoretically justified quantification of the agreement among ensembles of sensors, both overall for a sensor collection, and also at a fine-grained level specifying pairwise and multi-way interactions among sensors. We demonstrate that the theory of mathematical sheaves provides a unified answer to this need, supporting both quantitative and qualitative data. Furthermore, the theory provides algorithms to globalize data across the network of deployed sensors, and to diagnose issues when the data do not globalize cleanly. We demonstrate and illustrate the utility of sheaf-based tracking models based on experimental data of a wild population of black bears in Asheville, North Carolina. A measurement model involving four sensors deployed among the bears and the team of scientists charged with tracking their location is deployed. This provides a sheaf-based integration model which is small enough to fully interpret, but of sufficient complexity to demonstrate the sheaf’s ability to recover a holistic picture of the locations and behaviors of both individual bears and the bear-human tracking system. A statistical approach was developed in parallel for comparison, a dynamic linear model which was estimated using a Kalman filter. This approach also recovered bear and human locations and sensor accuracies. When the observations are normalized into a common coordinate system, the structure of the dynamic linear observation model recapitulates the structure of the sheaf model, demonstrating the canonicity of the sheaf-based approach. However, when the observations are not so normalized, the sheaf model still remains valid.

97 MATHEMATICS AND COMPUTING↗

Molecular dynamics simulation studies of 1,3-dimethyl imidazolium nitrate ionic liquid with water

The fundamental understanding of intermolecular interactions of ionic liquids (ILs) with water is essential in predicting IL–water thermodynamic properties. In this study, intermolecular or noncovalent interactions were studied for 1,3-dimethyl imidazolium [DMIM]+ cation and nitrate [NO 3 ] – anion with water, employing quantum mechanics and molecular dynamics simulations. Molecular dynamics simulations were performed using a revised multipolar polarizable force field. The effect of water on ionic liquids was evaluated in terms of thermodynamic and dynamic properties. Thermodynamic properties included liquid densities ρ, excess molar volumes ΔV E , and liquid structures g(r)⁠. Dynamic properties included self-diffusion coefficients D of mixture constituents as a function of water concentration. The density of ionic liquid–water mixtures monotonically decrease with increasing concentration of water. A negative excess volume was obtained for low and high water concentrations, demonstrating strong intermolecular interactions of water with ionic liquid components. Liquid structures of ionic liquid–water mixtures revealed a tendency for anions to interact with cations at shorter intermolecular distances when the water concentration is increased. Diffusion rates were found to increase for all mixture components with increase in the fraction of water. A significant change in the diffusion rate was found at ~0.3 weight fraction of water. However, the water self-diffusion coefficient was dominant at all concentrations. Furthermore, the ratio of water/anion and anion/cation self-diffusion coefficients was found to decrease linearly with increasing concentration of water molecules.

36 MATERIALS SCIENCE↗

Exploration of Tertiary Structure in Sequence-Defined Polymers Using Molecular Dynamics Simulations

Peptoids are a class of sequence-defined biomimetic polymers with peptide-like backbones and side chains located on backbone nitrogens rather than alpha carbons. These materials demonstrate a strong ability for precise control of single-chain structure, multiunit self-assembly, and macromolecular assembly through careful tuning of sequence due to the diversity of available side chains, although the driving forces behind these assemblies are often not understood. Prior experimental work has shown that linked 15mer peptoids can mimic the protein helical hairpin structure by leveraging the chirality-inducing nature of bulky side chains and hydrophobicity, but there are still gaps in our understanding of the relationship between sequence, stability, and particular secondary or tertiary structure. Here, we present a molecular dynamics (MD) study on the folding behavior of these polymers into hairpins, discussing the differences in structure from sequences with various characteristics in water and acetonitrile, and then compare the handedness preference of common helical motifs between solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Time-resolved atomic-resolution Brownian tomography of single nanocrystals reveals size-dependent dynamics

Atomic-resolution structure identification of nanocrystals by graphene liquid cell electron microscopy (GLC-EM) has revealed that small, solubilized platinum nanocrystals consist of an ordered crystalline core surrounded by mobile surface atoms, which dissociate during oxidative etching, resulting in distinct temporal structural states. Requirements imposed by the 3D reconstruction algorithm limit the number of structural states that can be resolved. We introduce a regularized 3D reconstruction algorithm that exploits the redundancy inherent in the experimental data, allowing us to improve the time resolution. Our developments provide a comprehensive molecular picture at unprecedented spatial and temporal resolution of the nonlinear, linear, and fluctuating dynamic phenomena that single nanocrystals undergo during the GLC-EM experiment. We determined atomic structures of 66 temporal structural states, extracted from 15 time trajectories of individual nanocrystals. Large (478 to 698 atoms) and small (<300 atoms) nanocrystals show etching that preserves a stable core, whereas mid-sized (351 to 571 atoms) nanocrystals present dynamics that change the coordination of the core.

Meana-Pañeda, Rubén↗

Re-entrant unconventional superconductivity induced by rare-earth substitution in Nd 1-x Eu x NiO 2 thin films

High temperature superconductivity is typically associated with strong coupling and a large superconducting gap, yet these characteristics have not been demonstrated in the nickelates. Here, we provide experimental evidence that Eu substitution in the spacer layer of Nd 1-x Eu x NiO 2 (NENO) thin films enhances the superconducting gap, driving the system toward a strong-coupling regime. This is accompanied by a magnetic-exchange-driven magnetic-field-enhanced superconductivity. We investigate the upper critical magnetic field, H c2 , and the superconducting gap of superconducting NENO thin films with x = 0.2 to 0.35. Magnetoresistance measurements reveal magnetic-field-enhanced superconductivity in NENO films. We interpret this phenomenon as a result of an interaction between magnetic Eu ions and superconducting states in the Ni d x2-y2 orbital. The upper critical magnetic field strongly violates the weak-coupling Pauli limit. Infrared spectroscopy confirms a large gap-to-Tc ratio $2\Delta /{k}_{B}{T}_{{\rm{c}}}\simeq 5-6$, indicating a stronger coupling pairing mechanism in NENO relative to the Sr-doped NdNiO 2 . The substitution of Eu in the rare-earth layer causes pronounced modifications of the superconducting gap and magnetic interactions in Nd-based nickelates, opening new pathways to engineer high- T c superconductivity in infinite-layer nickelates.

36 MATERIALS SCIENCE↗

Modeling of the Coral Microbiome: the Influence of Temperature and Microbial Network

Host-associated microbial communities are shaped by extrinsic and intrinsic factors to the holobiont organism. Environmental factors and microbe-microbe interactions act simultaneously on the microbial community structure, making the microbiome dynamics challenging to predict. The coral microbiome is essential to the health of coral reefs and sensitive to environmental changes. Here, we develop a dynamic model to determine the microbial community structure associated with the surface mucus layer (SML) of corals using temperature as an extrinsic factor and microbial network as an intrinsic factor. The model was validated by comparing the predicted relative abundances of microbial taxa to the relative abundances of microbial taxa from the sample data. The SML microbiome from Pseudodiploria strigosa was collected across reef zones in Bermuda, where inner and outer reefs are exposed to distinct thermal profiles. A shotgun metagenomics approach was used to describe the taxonomic composition and the microbial network of the coral SML microbiome. By simulating the annual temperature fluctuations at each reef zone, the model output is statistically identical to the observed data. The model was further applied to six scenarios that combined different profiles of temperature and microbial network to investigate the influence of each of these two factors on the model accuracy. The SML microbiome was best predicted by model scenarios with the temperature profile that was closest to the local thermal environment, regardless of the microbial network profile. Our model shows that the SML microbiome of P. strigosa in Bermuda is primarily structured by seasonal fluctuations in temperature at a reef scale, while the microbial network is a secondary driver. Coral microbiome dysbiosis (i.e., shifts in the microbial community structure or complete loss of microbial symbionts) caused by environmental changes is a key player in the decline of coral health worldwide. Multiple factors in the water column and the surrounding biological community influence the dynamics of the coral microbiome. However, by including only temperature as an external factor, our model proved to be successful in describing the microbial community associated with the surface mucus layer (SML) of the coral P. strigosa. The dynamic model developed and validated in this study is a potential tool to predict the coral microbiome under different temperature conditions.

59 BASIC BIOLOGICAL SCIENCES↗

Cavity-altered superconductivity

Is it feasible to alter the ground-state properties of a material by engineering its electromagnetic environment? Inspired by theoretical predictions, experimental realizations of such cavity-controlled properties without optical excitation are beginning to emerge. Here we devised and implemented a new platform to realize cavity-altered materials. Single crystals of hyperbolic van der Waals (vdW) compounds provide a resonant electromagnetic environment with enhanced density of photonic states and prominent mode confinement. We interfaced hexagonal boron nitride (hBN) with the molecular superconductor κ-(BEDT-TTF) 2 Cu[N(CN) 2 ]Br (κ-ET). The frequencies of infrared hyperbolic modes (HMs) of hBN match the infrared-active carbon–carbon (C=C) stretching molecular resonance of κ-ET implicated in superconductivity. Nano-optical data supported by first-principles molecular Langevin dynamics simulations confirm the presence of resonant coupling between the hBN hyperbolic cavity modes and the C=C stretching mode in κ-ET. Meissner-effect measurements using magnetic force microscopy (MFM) demonstrate a strong suppression of superfluid density near the hBN/κ-ET interface. Non-resonant control heterostructures, including RuCl 3 /κ-ET and hBN/Bi 2 Sr 2 CaCu 2 O 8+x (BSCCO), do not show the pronounced superfluid suppression. These observations suggest that hBN/κ-ET realizes a cavity-altered superconducting ground state. Our work highlights the potential of dark cavities devoid of external photons for engineering electronic ground-state properties of complex quantum materials.

36 MATERIALS SCIENCE↗

Patchy particle model of hydrated amorphous silica

Glasses corroded in static aqueous conditions typically reach a slow, residual rate of dissolution as a result of the complex interplay between multiple processes. While intrinsically suited to address this problem, Monte Carlo (MC) models developed to date have relied on lattices to describe the amorphous structure of glass and are thus unable to reproduce the residual rate of glass corrosion. A recently developed MC approach based on amorphous structures derived from molecular dynamics simulations offers a solution [Kerisit and Du J. Non-Cryst. Solids 522 (2019) 119601], but it requires a simple model that can rapidly relax the glass-water interface upon each dissolution/condensation event to retain the ability of MC simulations to reach large spatial and temporal scales. To this end, a patchy particle model of hydrated amorphous silica was developed and evaluated against atomistic simulations in this work. Models of water and amorphous silica were first developed separately, and cross terms were then defined to enable simulations of hydrated amorphous silica structures with varying water content. While the nature of its interaction potential prevents the patchy particle model from reproducing simultaneously the structure and dynamics of the systems of interest with a single set of parameters, it described well the connectivity of hydrated amorphous silica structures and the local coordination geometry of individual species. Therefore, this model opens the door to MC simulations of the residual rate of glass corrosion and offers an alternative to atomistic models to investigate the evolution of silica gels over large spatial and temporal scales.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗