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At least 217 records · Page 12

Nonadiabatic molecular dynamics analysis of hybrid Dion–Jacobson 2D leads iodide perovskites

The past six years have witnessed the rapid growth of interest in Dion–Jacobson (DJ) phase two-dimensional (2D) hybrid halide perovskites as optoelectronic materials with considerable intrinsic stability. The precise relationships between structural variations and the resulting charge carrier dynamics at finite temperature in these materials are keys to practical applications and are not yet completely understood. Here, we study 3-(aminomethyl) piperidinium (3AMP) and 4-(aminomethyl) piperidinium (4AMP) spacer cation-based lead iodide DJ phase systems and find these spacer cations to have a profound impact on the structural dynamics. Particularly, large conformational dynamics of the 3AMP-based perovskite compared to that of the 4AMP at room temperature leads to pronounced state energy fluctuation near band edges and further results in a shorter quantum coherence. The faster quantum decoherence of the 3AMP spacer-based perovskite underpins a longer nonradiative lifetime, offering insight into its superior performance as an optoelectronic material. This work sheds light on the relationship between structural fluctuations and charge carrier dynamics that can help in designing 2D perovskites with superior photophysical properties.

Wang, Ying (ORCID:0000000349048227)↗

Equatorial Dynamics Observed by Rocket, Radar, and Satellite During the CADRE/MALTED Campaign: Programmatics and small-scale fluctuations - 1

In August 1994, the Mesospheric and Lower Thermospheric Equatorial Dynamics (MALTED) Program was conducted from the Alcantara rocket site in northeastern Brazil as part of the International Guard Rocket Campaign to study equatorial dynamics, irregularities, and instabilities in the ionosphere. This site was selected because of its proximity to the geographic (2.3 deg S) and magnetic (approx. 0.5 deg S) equators. MALTED was concerned with planetary wave modulation of the diurnal tidal amplitude, which exhibits considerable amplitude variability at equatorial and subtropical latitudes. Our goals were to study this global modulation of the tidal motions where tidal influences on the thermal structure are maximum, to study the interaction of these tidal structures with gravity waves and turbulence at mesopause altitudes, and to gain a better understanding of dynamic influences and variability on the equatorial middle atmosphere. Four (two daytime and two nighttime) identical Nike-Orion payloads designed to investigate small-scale turbulence and irregularities were coordinated with 20 meteorological falling-sphere rockets designed to measure temperature and wind fields during a 10-day period. These in situ measurements were coordinated with observations of global-scale mesospheric motions that were provided by various ground based radars and the Upper Atmosphere Research Satellite (UARS) through the Coupling and Dynamics of Regions Equatorial (CADRE) campaign. The ground-based observatories included the Jicamarca radar observatory near Lima, Peru, and medium frequency (MF) radars in Hawaii, Christmas Island, and Adelaide. Since all four Nike-Orion flights penetrated and overflew the electrojet with apogees near 125 km, these flights provided additional information about the electrodynamics and irregularities in the equatorial ionospheric E region and may provide information on wave coupling between the mesosphere and the electrojet. Simultaneous with these flights, the CUPRI 50-MHz radar (Cornell University) provided local sounding of the electrojet region. A description of the campaign logistics and the measurements performed with the Nike-Orion instrumentation and their implications for turbulence due to gravity waves and tidal instability in the mesosphere and lower thermosphere (MLT) are presented here. From a study of electron density fluctuations measured by rocket probes, we have found evidence for equatorial mesospheric neutral-atmospheric turbulence between 85 and 90 km. Furthermore, falling-sphere data imply that gravity wave breaking was a source for this turbulence. Mean motions and the various planetary, tidal, and gravity wave structures and their coherence and variability are the subjects of a companion paper.

Goldberg, Richard A.↗

Thermal coupling-decoupling mechanism of heat transfer across van der Waals interfaces in n-eicosane

Progress toward improving thermal transport properties of n-eicosane, a promising phase change material for thermal energy storage near human body temperature, is hindered by lack of a general theoretical framework to model thermal interfacial conductance (TIC) of the van der Waals (vdW) force bonded molecular interfaces, which have little compositional/structural mismatch. Combining molecular dynamics simulations at temperatures up to the melting point and a time-domain analysis of interfacial heat currents in individual molecules, we unveil that (1) the heat flux across a molecular vdW interface has an alternating coupling-decoupling pattern at the single molecule level due to thermal fluctuations, and (2) the net heat transfer during the thermally coupled periods is orders of magnitude larger than that during the thermally decoupled periods. Furthermore, we demonstrate that a vdW interface's TIC correlates almost linearly with two atomistic-scale coupling-decoupling parameters: αc and σc, that represent the duration and strength of the thermal coupling, respectively. This thermal coupling-decoupling mechanism proposes a new paradigm that explicitly accounts for the effects of structural flexibility and dynamical fluctuation on heat transfer across molecular interfaces, and will likely provide new insights into modeling thermal transport properties in a wide-ranging soft materials, including self-assembled monolayers, paraffins or lipids.

42 ENGINEERING↗

Drivers of Natural Variation in Water-Use Efficiency Under Fluctuating Light Are Promising Targets for Improvement in Sorghum

Improving leaf intrinsic water-use efficiency ( iWUE ), the ratio of photosynthetic CO 2 assimilation to stomatal conductance, could decrease crop freshwater consumption. iWUE has primarily been studied under steady-state light, but light in crop stands rapidly fluctuates. Leaf responses to these fluctuations substantially affect overall plant performance. Notably, photosynthesis responds faster than stomata to decreases in light intensity: this desynchronization results in substantial loss of iWUE . Traits that could improve iWUE under fluctuating light, such as faster stomatal movement to better synchronize stomata with photosynthesis, show significant natural diversity in C 3 species. However, C 4 crops have been less closely investigated. Additionally, while modification of photosynthetic or stomatal traits independent of one another will theoretically have a proportionate effect on iWUE , in reality these traits are inter-dependent. It is unclear how interactions between photosynthesis and stomata affect natural diversity in iWUE , and whether some traits are more tractable drivers to improve iWUE . Here, measurements of photosynthesis, stomatal conductance and iWUE under steady-state and fluctuating light, along with stomatal patterning, were obtained in 18 field-grown accessions of the C 4 crop sorghum. These traits showed significant natural diversity but were highly correlated, with important implications for improvement of iWUE . Some features, such as gradual responses of photosynthesis to decreases in light, appeared promising for improvement of iWUE . Other traits showed tradeoffs that negated benefits to iWUE , e.g., accessions with faster stomatal responses to decreases in light, expected to benefit iWUE , also displayed more abrupt losses in photosynthesis, resulting in overall lower iWUE . Genetic engineering might be needed to break these natural tradeoffs and achieve optimal trait combinations, e.g., leaves with fewer, smaller stomata, more sensitive to changes in photosynthesis. Traits describing iWUE at steady-state, and the change in iWUE following decreases in light, were important contributors to overall iWUE under fluctuating light.

54 ENVIRONMENTAL SCIENCES↗

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↗

Ground-to-Ground Optical Communications Demonstration

A bidirectional horizontal-path optical link was demonstrated between Strawberry Peak (SP), Lake Arrowhead, California, and the JPL Table Mountain Facility (TMF), Wrightwood, California, during June and November of 1998. The 0.6-m telescope at TMF was used to broadcast a 4-beam 780-nm beacon to SP. The JPL-patented Optical Communications Demonstrator (OCD) at SP received the beacon, performed ne tracking to compensate for the atmosphere-induced beacon motion and retransmitted a 844-nm communications laser beam modulated at 40 to 500 Mb/s back to TMF. Characteristics of the horizontal-path atmospheric channel as well as performance of the optical communications link were evaluated. The normalized variance of the irradiance fluctuations or scintillation index delta2/I at either end was determined. At TMF where a single 844-nm beam was received by a 0.6-m aperture, the measured delta2/I covered a wide range from 0.07 to 1.08. A single 780-nm beam delta2/I measured at SP using a 0.09-m aperture yielded values ranging from 0.66 to 1.03, while a combination of four beams reduced the scintillation index due to incoherent averaging to 0.22 to 0.40. This reduction reduced the dynamic range of the fluctuations from 17 to 21 dB to 13 to 14 dB as compared with the OCD tracking sensor dynamic range of 10 dB. Predictions of these values also were made based on existing theories and are compared. Generally speaking, the theoretical bounds were reasonable. Discussions on the probability density function (PDF) of the intensity fluctuations are presented and compared with the measurements made. The lognormal PDF was found to agree for the weak scintillation regime as expected. The present measurements support evidence presented by earlier measurements made using the same horizontal path, which suggests that the aperture averaging effect is better than theoretically predicted.

Biswas, A.↗

MD Simulation of Water Using a Rigid Body Description Requires a Small Time Step to Ensure Equipartition

In simulations of aqueous systems, it is common to freeze the bond vibration and angle bending modes in water to allow for a longer time step δt for integrating the equations of motion. Thus, δt = 2 fs is often used in simulating rigid models of water. We simulate the SPC/E model of water using δt from 0.5 to 3.0 fs and up to 4 fs using hydrogen mass repartitioning. In these simulations, we find that for all but δt = 0.5 fs, equipartition is not obtained between translational and rotational modes, with the rotational modes exhibiting a lower temperature than the translation modes. To probe the reasons for the lack of equipartition, we study the autocorrelation of the translational velocity of the center of mass and the angular velocity of the rigid water molecule, respectively. Here, we find that the rotational relaxation occurs on a timescale comparable to vibrational periods, calling into question the original motivations for freezing the vibrations. Furthermore, a time step with δt ≥ 1 fs is not able to capture accurately the fast rotational relaxation, which reveals its impact as an effective slowing-down of rotational relaxation. The fluctuation–dissipation relation then leads to the conclusion that the rotational temperature should be cooler for δt greater than the reference value of 0.5 fs. Consideration of fluctuation–dissipation in equilibrium molecular dynamics simulations also emphasizes the need to capture the temporal evolution of fluctuations with fidelity and the role of δt in this regard. The time step also influences the solution thermodynamic properties: both the mean system potential energies and the excess entropy of hydration of a soft repulsive cavity are sensitive to δt.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum fluctuations drive nonmonotonic correlations in a qubit lattice

Abstract Fluctuations may induce the degradation of order by overcoming ordering interactions, consequently leading to an increase of entropy. This is particularly evident in magnetic systems characterized by nontrivial, constrained disorder, where thermal or quantum fluctuations can yield counterintuitive forms of ordering. Using the proven efficiency of quantum annealers as programmable spin system simulators, we present a study based on entropy postulates and experiments on a platform of programmable superconducting qubits to show that a low level of uncertainty can promote ordering in a system impacted by both thermal and quantum fluctuations. A set of experiments is proposed on a lattice of interacting qubits arranged in a triangular geometry with precisely controlled disorder, effective temperature, and quantum fluctuations. Our results demonstrate the creation of ordered ferrimagnetic and layered anisotropic disordered phases, displaying characteristics akin to the elegant order-by-disorder phenomenon. Extensive experimental evidence is provided for the role of quantum fluctuations in lowering the total energy of the system by increasing entropy and defect clustering. Our thorough and comprehensive application of an intentionally introduced noise on a quantum platform provides insight into the dynamics of defects and fluctuations in quantum devices, which may help to reduce the cost associated with quantum processing.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Cluster spin glass correlations and dynamics in Zn 0.5⁢ Mn 0.5⁢ Te

Here, we present a combined magnetometry, muon spin-relaxation (𝜇⁢SR), and neutron-scattering study of the insulating spin glass Zn 0.5 ⁢Mn 0.5 ⁢Te, for which magnetic Mn 2+ and nonmagnetic Zn 2+ ions are randomly distributed on a face-centered cubic lattice. The magnetometry and 𝜇⁢SR results confirm a spin freezing transition around 𝑇 𝑓 ≈ 23 K, with the spin-fluctuation rate decreasing gradually and somewhat inhomogeneously through the sample volume as the temperature decreases toward 𝑇 𝑓 . Characteristic spin-correlation times well above 𝑇 𝑓 are on the order of 10 −10 s, much slower than typically observed in canonical spin glasses but in line with expectations for a cluster spin glass. Using magnetic pair distribution function (mPDF) analysis and reverse Monte Carlo (RMC) modeling of the magnetic diffuse neutron-scattering data, we show that the spin-glass ground state consists of clusters of spins exhibiting short-range-ordered type-III antiferromagnetic correlations with a locally ordered moment of 3.1⁢(1)⁢𝜇 B between nearest-neighbor spins. The type-III correlations decay exponentially as a function of spin separation distance with a correlation length of approximately 5 Å. The diffuse magnetic scattering and corresponding mPDF show no significant changes across 𝑇 𝑓 , indicating that the dynamically fluctuating short-range spin correlations in the paramagnetic state retain the same basic type-III configuration that characterizes the spin-glass state; the only change apparent from the neutron-scattering data is a gradual reduction of the correlation length and locally ordered moment with increasing temperature. Taken together, these results paint a unique and detailed picture of the local magnetic structure and dynamics in Zn 0.5 ⁢Mn 0.5⁢ Te and provide strong evidence that this material is best described as a cluster spin glass. In addition, this work showcases a statistical method for extracting diffuse scattering signals from neutron powder diffraction data, which we developed to facilitate the mPDF and RMC analysis of the neutron data. This method has the potential to be broadly useful for neutron powder diffraction experiments on a variety of materials with short-range atomic or magnetic order.

magnetism↗

Driven probe particle dynamics in a bubble and pattern forming system

We numerically examine the dynamics of a probe particle driven at a constant force through an assembly of particles with competing long-range repulsion and short-range attraction that forms a bubble or stripe state. In the bubble regime, we identify several distinct types of motion, including an elastic or pinned regime where the probe particle remains inside a bubble and drags all other bubbles with it. There is also a plastic bubble phase where the bubble in which the probe particle is trapped is able to move past the adjacent bubbles. At larger drives, there is a breakthrough regime where the probe particle jumps from bubble to bubble and, in some cases, can induce correlated rotations or plastic rearrangements of the particles within the bubbles. At the highest drives, the probe particle moves sufficiently rapidly that the background particles undergo only small distortions. The distinctive dynamic flow states and the transitions between them are accompanied by signatures in the effective drag on the driven particle, jumps in the velocity–force curves, and changes in the time-dependent velocity fluctuations. We map the dynamic phase diagram for this system for varied interaction lengths, bubble sizes, and densities.

36 MATERIALS SCIENCE↗

The effect of the dynamic wet troposphere on VLBI measurements

Calculations using a statistical model of water vapor fluctuations yield the effect of the dynamic wet troposphere on Very Long Baseline Interferometry (VLBI) measurements. The statistical model arises from two primary assumptions: (1) the spatial structure of refractivity fluctuations can be closely approximated by elementary (Kolmogorov) turbulence theory, and (2) temporal fluctuations are caused by spatial patterns which are moved over a site by the wind. The consequences of these assumptions are outlined for the VLBI delay and delay rate observables. For example, wet troposphere induced rms delays for Deep Space Network (DSN) VLBI at 20-deg elevation are about 3 cm of delay per observation, which is smaller, on the average, than other known error sources in the current DSN VLBI data set. At 20-deg elevation for 200-s time intervals, water vapor induces approximately 1.5 x 10 to the minus 13th power s/s in the Allan standard deviation of interferometric delay, which is a measure of the delay rate observable error. In contrast to the delay error, the delay rate measurement error is dominated by water vapor fluctuations. Water vapor induced VLBI parameter errors and correlations are calculated. For the DSN, baseline length parameter errors due to water vapor fluctuations are in the range of 3 to 5 cm. The above physical assumptions also lead to a method for including the water vapor fluctuations in the parameter estimation procedure, which is used to extract baseline and source information from the VLBI observables.

Treuhaft, R. N.↗

Fluctuating hydrodynamics and the Rayleigh–Plateau instability

The Rayleigh–Plateau instability occurs when surface tension makes a fluid column become unstable to small perturbations. At nanometer scales, thermal fluctuations are comparable to interfacial energy densities. Consequently, at these scales, thermal fluctuations play a significant role in the dynamics of the instability. These microscopic effects have previously been investigated numerically using particle-based simulations, such as molecular dynamics (MD), and stochastic partial differential equation–based hydrodynamic models, such as stochastic lubrication theory. In this paper, we present an incompressible fluctuating hydrodynamics model with a diffuse-interface formulation for binary fluid mixtures designed for the study of stochastic interfacial phenomena. An efficient numerical algorithm is outlined and validated in numerical simulations of stable equilibrium interfaces. We present results from simulations of the Rayleigh–Plateau instability for long cylinders pinching into droplets for Ohnesorge numbers of Oh = 0.5 and 5.0. Both stochastic and perturbed deterministic simulations are analyzed and ensemble results show significant differences in the temporal evolution of the minimum radius near pinching. Short cylinders, with lengths less than their circumference, were also investigated. As previously observed in MD simulations, we find that thermal fluctuations cause these to pinch in cases where a perturbed cylinder would be stable deterministically. Finally, we show that the fluctuating hydrodynamics model can be applied to study a broader range of surface tension–driven phenomena.

97 MATHEMATICS AND COMPUTING↗

DE-2 cusp observations - Role of plasma instabilities in topside ionospheric heating and density fluctuations

Observations by the low altitude Dynamics Explorer satellite (DE-2) in the polar cusp show the ionospheric plasma electron temperature and the ratio of electron to ion temperature to be increased, and the electron density fluctuations to be enhanced. Also, downward fluxes of energetic eletrons and ions increase in the cusp, and the magnetic field structure are consistent with the existence of a field-aligned current. Simultaneously, there is characteristic broadband electrostatic noise (BEN) with amplitudes of 1-10 mV/m, peaking in the cusp but extending into the polar cap. These emissions range from far below the local 0(+) gyrofrequency F sub O(+) to the vicinity of the proton gyrofrequency, but below the oxygen lower hybrid frequency. The BEN observations are compared to the predictions of several theories. The amplitude of these waves is shown to be far too small to contribute significantly to the observed ionospheric heating or density fluctuations by local wave-particle interactions. Rather, the observed spatial variations are attributed to nonlocal field aligned heating processes and reflect the nonuniformity of the magnetosheath plasma's penetration into the ionosphere.

Curtis, S. A.↗

Correlated anharmonicity and dynamic disorder control carrier transport in halide perovskites

Halide pervoskites are an important class of semiconducting materials that hold great promise for optoelectronic applications. In this work we investigate the relationship between vibrational anharmonicity and dynamic disorder in this class of solids. Via a multiscale model parametrized from first-principles calculations, we demonstrate that the non-Gaussian lattice motion in halide perovskites is microscopically connected to the dynamic disorder of overlap fluctuations among electronic states. This connection allows us to rationalize the emergent differences in temperature-dependent mobilities of prototypical MAPbI 3 and MAPbBr 3 compounds across structural phase transitions, in agreement with experimental findings. In conclusion, our analysis suggests that the details of vibrational anharmonicity and dynamic disorder can complement known predictors of electronic conductivity and can provide structure-property guidelines for the tuning of carrier transport characteristics in anharmonic semiconductors.

36 MATERIALS SCIENCE↗

Low Mach number two-dimensional hydrodynamic turbulence - Energy budgets and density fluctuations in a polytropic fluid

Theory suggests that three distinct types of turbulence can occur in the low Mach number limit of polytropic flow: nearly incompressible flows dominated by vorticity, nearly pure acoustic turbulence dominated by compression, and flows characterized by near statistical equipartition of vorticity and compressions. Distinctions between these kinds of turbulence are investigated here by direct numerical simulation of two-dimensional compressible hydrodynamic turbulence. Dynamical scalings of density fluctuations, examination of the ratio of transverse to longitudinal velocity fluctuations, and spectral decomposition of the fluctuations are employed to distinguish the nature of these low Mach number solutions. A strong dependence on the initial data is observed, as well as a tendency for enhanced effects of compressibility at later times and at higher wave numbers, as suggested by theories of nearly incompressible flows.

Ghosh, S.↗

Laplace-transform technique for deriving thermodynamic equations from the classical microcanonical ensemble

A direct and convenient method is presented for deriving expressions which equate any thermodynamic state function to averages of specific dynamical functions and their fluctuations over the classical microcanonical distribution. Specific expressions are obtained for a variety of thermodynamic quantities. The effect of various entropy definitions on the results are assessed, and the latter are compared to previous work in the literature. The derived formulas are applied to the analysis of molecular-dynamics computer simulations.

Pearson, E. M.↗

Noncentrosymmetric Triangular Magnet CaMnTeO 6 : Strong Quantum Fluctuations and Role of s 0 versus s 2 Electronic States in Competing Exchange Interactions

Abstract Noncentrosymmetric triangular magnets offer a unique platform for realizing strong quantum fluctuations. However, designing these quantum materials remains an open challenge attributable to a knowledge gap in the tunability of competing exchange interactions at the atomic level. Here, a new noncentrosymmetric triangular S = 3/2 magnet CaMnTeO 6 is created based on careful chemical and physical considerations. The model material displays competing magnetic interactions and features nonlinear optical responses with the capability of generating coherent photons. The incommensurate magnetic ground state of CaMnTeO 6 with an unusually large spin rotation angle of 127°(1) indicates that the anisotropic interlayer exchange is strong and competing with the isotropic interlayer Heisenberg interaction. The moment of 1.39(1) µB , extracted from low‐temperature heat capacity and neutron diffraction measurements, is only 46% of the expected value of the static moment 3 µB . This reduction indicates the presence of strong quantum fluctuations in the half‐integer spin S = 3/2 CaMnTeO 6 magnet, which is rare. By comparing the spin‐polarized band structure, chemical bonding, and physical properties of AMnTeO 6 ( A = Ca, Sr, Pb), how quantum‐chemical interpretation can illuminate insights into the fundamentals of magnetic exchange interactions, providing a powerful tool for modulating spin dynamics with atomically precise control is demonstrated.

36 MATERIALS SCIENCE↗