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At least 1,513 records · Page 84

Saddle point approaches in strong field physics and generation of attosecond pulses

Attoscience is the emerging field that accesses the fastest electronic processes occurring at the atomic and molecular length scales with attosecond (1 as = 10 –18 s) time resolution having wide ranging physical, chemical, material science and biological applications. The quintessential and one of the most fundamental processes in this domain is the generation of phase locked XUV attosecond pulses. The theoretical approach to understand the process incorporates a fully quantum or semi classical or relativistic description of coherent charge dynamics in intense ultrashort electromagnetic fields driving a quantum system (an atom, a molecule, solid band gap materials or surface plasmas). Modelling of such physical and dynamical systems in science and also in many other branches often leads to equations represented in terms of complex multi-dimensional integrals. These integrals can often be solved using the stationary phase approximation, which leads to a series of equations identifying the points in the multi-dimensional space, having most significant contributions in their evaluation. These points are usually indicated as saddle points. The description of the dynamics of quantum mechanical or relativistic systems that results from such an approach enables near to classical physics intuitive perceptions of the processes under investigation. Thus, the saddle point methods are very powerful and valuable general theoretical tools to obtain asymptotic expressions of such solutions and help also to gain physical insights on the underlying phenomena. Such techniques developed in the past have been adapted to study the emission of as pulses by different physical systems and have been widely employed in calculating and estimating the response of matter to intense electromagnetic pulses on ultrafast time scales. Here we provide an extensive disposition of the saddle point approaches unifying their ubiquitous applications within the domain of attoscience valid for simple atomic to more complex condensed matter systems undergoing ultrafast dynamics and present current trends and advancements in the field. In this review we would delineate the methodology, present a synthesis of seminal works and describe the state of the art applications. Finally we also address ultrashort time dynamics of novel materials that have gained much attention recently, namely lower dimensional material systems and micro-plasma systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Nanoscale Probing of Dynamics in Local Molecular Environments

Vibrational spectroscopy can provide information about structure, coupling, and dynamics underlying the properties of complex molecular systems. While measurements of spectral line broadening can probe local chemical environments, the spatial averaging in conventional spectroscopies limits insight into underlying heterogeneity, in particular in disordered molecular solids. Here, using femtosecond infrared scattering scanning near-field optical microscopy (IR s-SNOM), we resolve in vibrational free-induction decay (FID) measurements a high degree of spatial heterogeneity in polytetrafluoroethylene (PTFE) as a dense molecular model system. In nanoscopic probe volumes as small as 103 vibrational oscillators, we approach the homogeneous response limit, with extended vibrational dephasing times of several picoseconds, that is, up to 10 times the inhomogeneous lifetime, and spatial average converging to the bulk ensemble response. We simulate the dynamics of relaxation with a finite set of local vibrational transitions subject to random modulations in frequency. The combined results suggest that the observed heterogeneity arises due to static and dynamic variations in the local molecular environment. This approach thus provides real-space and real-time visualization of the subensemble dynamics that define the properties of many functional materials.

Atkin, Joanna M.↗

Guest-Induced Large and Tunable Negative Thermal Expansion in Soft Microporous Carbon

Materials that exhibit negative thermal expansion (NTE) are of fundamental interest due to their rarity and counterintuitive behavior. While research in this area has been directed toward the discovery of materials that display NTE and explaining its origin, there has been less attention to describing the complexities of a secondary phase or other guests that could influence the magnitude and mechanism of NTE. We report herein that zeolite-templated carbon (ZTC), a soft carbonaceous framework solid with ordered microporosity, exhibits a large and widely tunable thermal expansion in the presence of adsorbed guests. For ZTC in the presence of CO 2 at 1 bar, the largest coefficient of isotropic NTE ever observed (−8.4 × 10 –4 K –1 ) is measured between 200 and 220 K. These results comprise a tunable mechanism of thermal expansion based on the interaction between two independent, positively expanding phases that together give rise to an anomalous guest-induced NTE under certain conditions.

03 NATURAL GAS↗

Structure and properties of densified silica glass: characterizing the order within disorder

The broken symmetry in the atomic-scale ordering of glassy versus crystalline solids leads to a daunting challenge to provide suitable metrics for describing the order within disorder, especially on length scales beyond the nearest neighbor that are characterized by rich structural complexity. Here, we address this challenge for silica, a canonical network-forming glass, by using hot versus cold compression to (i) systematically increase the structural ordering after densification and (ii) prepare two glasses with the same high-density but contrasting structures. The structure was measured by high-energy X-ray and neutron diffraction, and atomistic models were generated that reproduce the experimental results. The vibrational and thermodynamic properties of the glasses were probed by using inelastic neutron scattering and calorimetry, respectively. Traditional measures of amorphous structures show relatively subtle changes upon compacting the glass. The method of persistent homology identifies, however, distinct features in the network topology that change as the initially open structure of the glass is collapsed. The results for the same high-density glasses show that the nature of structural disorder does impact the heat capacity and boson peak in the low-frequency dynamical spectra. Densification is discussed in terms of the loss of locally favored tetrahedral structures comprising oxygen-decorated SiSi 4<:sub> tetrahedra.

36 MATERIALS SCIENCE↗

Co-doped sodium chloride crystals exposed to different irradiation temperature

Monocrystals of NaCl:XCl{sub 2}:MnCl{sub 2}(X = Ca,Cd) at four different concentrations have been analyzed. The crystals were exposed to different irradiation temperature, such as at room temperature (RT), solid water (SW), dry ice (DI) and liquid nitrogen (LN). The samples were irradiated with photon from {sup 60}Co irradiators. The co-doped sodium chloride crystals show a complex structure of glow curves that can be related to different distribution of traps. The linearity response was analyzed with the F(D) index. The F(D) value was less than unity indicating a sub-linear response was obtained from the TL response on the function of the dose. The glow curves were deconvoluted by using the CGCD program based on the first, second and general order kinetics.

36 MATERIALS SCIENCE↗

Acoustic force spectroscopy reveals subtle differences in cellulose unbinding behavior of carbohydrate-binding modules

Protein adsorption to solid carbohydrate interfaces is critical to many biological processes, particularly in biomass deconstruction. To engineer more-efficient enzymes for biomass deconstruction into sugars, it is necessary to characterize the complex protein–carbohydrate interfacial interactions. A carbohydrate-binding module (CBM) is often associated with microbial surface-tethered cellulosomes or secreted cellulase enzymes to enhance substrate accessibility. However, it is not well known how CBMs recognize, bind, and dissociate from polysaccharides to facilitate efficient cellulolytic activity, due to the lack of mechanistic understanding and a suitable toolkit to study CBM–substrate interactions. Our work outlines a general approach to study the unbinding behavior of CBMs from polysaccharide surfaces using a highly multiplexed single-molecule force spectroscopy assay. Here, we apply acoustic force spectroscopy (AFS) to probe a Clostridium thermocellum cellulosomal scaffoldin protein (CBM3a) and measure its dissociation from nanocellulose surfaces at physiologically relevant, low force loading rates. An automated microfluidic setup and method for uniform deposition of insoluble polysaccharides on the AFS chip surfaces are demonstrated. The rupture forces of wild-type CBM3a, and its Y67A mutant, unbinding from nanocellulose surfaces suggests distinct multimodal CBM binding conformations, with structural mechanisms further explored using molecular dynamics simulations. Applying classical dynamic force spectroscopy theory, the single-molecule unbinding rate at zero force is extrapolated and found to agree with bulk equilibrium unbinding rates estimated independently using quartz crystal microbalance with dissipation monitoring. However, our results also highlight critical limitations of applying classical theory to explain the highly multivalent binding interactions for cellulose–CBM bond rupture forces exceeding 15 pN.

09 BIOMASS FUELS↗

Effects of Field of View and Visual Complexity on Virtual Reality Training Effectiveness for a Visual Scanning Task

Virtual reality training systems are commonly used in a variety of domains, and it is important to understand how the realism of a training simulation influences training effectiveness. The paper presents a framework for evaluating the effects of virtual reality fidelity based on an analysis of a simulation’s display, interaction, and scenario components. Following this framework, we conducted a controlled experiment to test the effects of fidelity on training effectiveness for a visual scanning task. The experiment varied the levels of field of view and visual realism during a training phase and then evaluated scanning performance with the simulator’s highest level of fidelity. To assess scanning performance, we measured target detection and adherence to a prescribed strategy. The results show that both field of view and visual realism significantly affected target detection during training; higher field of view led to better performance and higher visual realism worsened performance. Additionally, the level of visual realism during training significantly affected learning of the prescribed visual scanning strategy, providing evidence that high visual realism was important for learning the technique. The results also demonstrate that task performance during training was not always a sufficient measure of mastery of an instructed technique. That is, if learning a prescribed strategy or skill is the goal of a training exercise, performance in a simulation may not be an appropriate indicator of effectiveness outside of training—evaluation in a more realistic setting may be necessary.

97 MATHEMATICS AND COMPUTING↗

High expression of PSF1 promotes drug resistance and cell cycle transit in leukemia cells

Abstract Escape of cancer cells from chemotherapy is a problem in the management of cancer patients. Research on chemotherapy resistance has mainly focused on the heterogeneity of cancer cells, multiple gene mutations, and quiescence of malignant cancer cells. However, some studies have indicated that interactions between cancer cells and vascular cells promote resistance to chemotherapy. Here, we established mouse leukemia models using the cell lines THP‐1 or MEG‐1. These were derived from acute and chronic myeloid leukemias, respectively, and highly expressed DNA replication factor PSF1, a member of the GINS complex. We found that, after anti‐cancer drug administration, surviving GFP‐positive leukemia cells in the bone marrow were located adjacent to blood vessels, as previously reported in a subcutaneous solid tumor transplantation model. Treating THP‐1 and MEG‐1 cells with anti‐cancer drugs in vitro revealed that those most strongly expressing PSF1 were most chemoresistant, suggesting that PSF1 induces not only cell cycle progression but also facilitates cell survival. Indeed, when PSF1 expression was suppressed by shRNA, the growth rate was reduced and cell death was enhanced in both cell lines. Furthermore, PSF1 knockdown in leukemia cells led to a change in their location at a distance from the blood vessels in a bone marrow transplantation model. These findings potentially reflect a mechanism of escape of leukemic cells from chemotherapy and suggest that PSF1 may be a possible therapeutic target to enhance the effect of chemotherapy.

Hsieh, Han‐Yun↗

Lagrangian simulations of spray interaction with a surface using a stochastic multi-regime impingement model

Modeling of spray impingement upon the piston or cylinder surface is important for hydrocarbon emission and soot predictions in high-fidelity simulation of internal combustion engines with direct injections. Due to the complexity of the physical process of spray impingement, current computational models heavily rely on the empirical studies which involve large uncertainties. A computational model is presented for spray impingement on solid walls in general computational fluid dynamics (CFD) simulations. The model adopts the Marmanis-Thoroddsen theory for determining the number of secondary droplets and a stochastic method for calculating the velocities of the secondary droplets. The numerical methods and parallel implementation of the impingement model are presented in detail. The model is implemented in Grit, which is a recently developed CPU/GPU performance-portable Lagrangian particle library, for accelerating spray simulations. The model and its implementation are tested for examples of spray impingements on flat and smooth surfaces with different impingement angles.

Ge, Wenjun↗

Modeling Heat Loss through Piston and Effects of Thermal Boundary Coatings in Diesel Engine Simulations using Conjugate Heat Transfer models

Heat loss through wall boundaries play a dominant role in the overall performance and efficiency of internal combustion engines. Typical engine simulations use constant temperature wall boundary conditions. These boundary conditions cannot be estimated accurately from experiments due to the complexities involved with engine combustion. As a result they introduce a large uncertainty in engine simulations and serve as a tuning parameter. Modeling the process of heat transfer through the solid walls in an unsteady engine computational fluid dynamics (CFD) simulation can lead to the development of higher fidelity engine calculations. These models can be used to study the impact of heat loss on engine efficiency and explore new design methodologies that can reduce heat losses. In this work, a single cylinder diesel engine is modeled along with the solid piston coupled to the fluid domain. Conjugate heat transfer (CHT) modeling techniques were implemented to model heat losses for a full cycle of a Navistar diesel engine. This CFD model is then validated against experimental data available from thermocouples embedded inside the piston surface. The overall predictions from the model match closely with the experimental observations. The validated model is further used to explore the benefits of thermal barrier coatings (TBC) on piston bowls. The effect of TBC coatings were modeled as a thermal resistance in the heat transfer models. Full cycle 3D engine simulations provide quantitative insights into heat loss and thus calculate the efficiency gain by the use of TBC coatings. The work establishes a validated modeling framework for CHT modeling in reciprocating engine simulations.

Kundu, Prithwish↗

CabanaPD

CabanaPD is a meshfree peridynamics application built with Cabana and Kokkos. Kokkos enables performance portability across hardware architectures and Cabana provides particle capabilities including multi-node MPI support. The main components of CabanaPD are particle initialization, neighbor list generation, force and energy computation, time integration, and multi-node particle communication. In addition, options for creating pre-cracked regions and particle boundary conditions are available. CabanaPD currently enables two common force models: prototype microelastic brittle (PMB) and linear peridynamic solid (LPS). For both of these models, versions with and without fracture as well as linearized model options are available. CabanaPD is designed to be extensible for addition of more complex force models, boundary conditions, etc.

Reeve, Sam↗

Trace Key Mechanistic Features of the Arsenite Sequestration Reaction with Nanoscale Zerovalent Iron

Nanoscale zerovalent iron (nZVI) is considered as a highly efficient material for sequestrating arsenite, but the origin of its high efficacy as well as the chemical transformations of arsenite during reaction is not well understood. Here, in this study, we report an in situ X-ray absorption spectroscopy (XAS) study to investigate the complex mechanism of nZVI reaction with arsenite under anaerobic conditions at the time scale from seconds to days. The time-resolved XAS analysis revealed a gradual oxidation of As III to As V in the course of minutes to hours in both the solid and liquid phase for the high (above 0.5 g/L) nZVI dose system. When the reaction time increased up to 60 days, As V became the dominant species. The quick-scanning extended X-ray absorption fine structure (QEAXFS) was introduced to discover the transient intermediate at the highly reactive stage, and a small red-shift in As K-edge absorption edge was observed. The QEAXFS combined with density functional theory (DFT) calculation suggested that the red-shift is likely due to the electron donation in a Fe-O-As complex and possible active sites of As sequestrations include Fe(OH) 4 and 4-Fe cluster. This is the first time that the transient reaction intermediate was identified in the As-nZVI sequestration system at the fast-reacting early stage. This study also demonstrated usefulness of in situ monitoring techniques in environmental water research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring Charge Transport and Magnetism in Complex Half-Heusler/Full-Heusler Nanocomposites (Final Report)

This project exploits (1) the facile co-crystallization of the half-Heusler (HH) and full-Heusler (FH) structures, (2) the high coherency and stability of the HH/FH interfaces, and (3) the solid-state inter-conversion between HH and FH structures through local atomic diffusion, to investigate, for selected compositions of the HH and FH phases, the effect of size, dimensionality, dispersion and volume fraction of FH nanostructures on the electronic, phonon and magnetic behavior of the resulting HH/FH nanocomposites. Our goal is to identify and control key material and growth parameters governing phase formation, microstructural evolution, and to understand the mechanism by which these changes of the internal structure modify the material’s performance. To elucidate the mechanism by which the FH nanostructures regulate electronic charge transport and induce ferromagnetism within non-magnetic and magnetic semiconducting HH matrices, suitable series of HH/0D-FH and HH/2D-FH nanocomposites will be fabricated using synthesis conditions suggested by theoretical calculations of the formation energy and stability of various FH phases (varying M) in HH matrices with known chemical composition. The structure of the HH/FH interfaces (size, chemical composition, volume fraction and dispersion) will be investigated along with the evaluation of the electronic (carrier density, mobility, thermopower, electrical conductivity, effective mass), thermal and magnetic (susceptibility, magnetization etc.) properties of the resulting HH/FH nanocomposites.

36 MATERIALS SCIENCE↗

Microstructure evolution of wrought nickel based superalloy GH4037 in the semi-solid state

Highlights: • Semi-solid isothermal treatment of wrought superalloy (SSITWS). • Near-globular microstructure. • Carbide precipitates. - Abstract: Study on semi-solid processing of superalloy is little reported due to the difficulties in fabricating semi-solid billets. In this manuscript, a novel method called semi-solid isothermal treatment of wrought superalloy (SSITWS) was firstly proposed in order to fabricate semi-solid billets of superalloy. The effects of isothermal temperature and soaking time on microstructure of Ni-based superalloy GH4037 in the semi-solid state were investigated. The results show that the near-globular microstructure of wrought GH4037 superalloy can be obtained by the semi-solid isothermal treatment. The average grain size increased and the roundness decreased with the prolonged soaking time at 1350 °C and 1360 °C. When the isothermal temperature was elevated to 1370 °C or 1380 °C, the microstructure evolution was complex due to the combination of breaking up mechanism and coarsening mechanism. At 1390 °C, the dendritic grains were obviously observed in the microstructure. With the increasing of isothermal temperature and soaking time, the liquid boundary film coarsening behavior occurred in the microstructure. With the increasing of soaking time, the size of intragranular liquid droplets increased, but the amount of them decreased. When the isothermal temperature was high, the intragranular liquid droplets disappeared. The coarsening rate constant at 1360 °C was lower compared to that at 1350 °C. However, when the isothermal temperature was higher than 1370 °C, the coarsening kinetics was not suitable for describing the microstructure evolution. The discrete carbide precipitates appeared in the grain boundaries. The distribution of Ti and Mo were higher in the grain boundaries than that in solid grains, and the distribution of other elements was homogenous in the grain boundaries and inside the grains.

36 MATERIALS SCIENCE↗

Bridging the Gap in Carbon Free Iron Making: How Hydrogen Affects the Reduction of Iron Ore between 900 and 1590 °C

Hydrogen-based reduction of iron ore for iron and steel production has emerged as a promising alternative to coal and natural gas. Unlike other hydrogen-based iron ore reduction studies, this research focuses on a wide temperature range across 900–1590 °C, encompassing reduction in solid, mixed, and liquid (slag) phases. For a 20 min exposure to hydrogen, the reduction degree increased monotonically from ∼35% at 900 °C to >90% at 1550 °C, except between 1100 °C and 1400 °C, where it stagnated ∼60%. This experimental work challenges the widely accepted notion that higher temperatures enhance the reduction process. Instead, it reveals an overlooked kinetic bottleneck, suggesting complex thermodynamic and mass transfer limitations influenced by phase transformations, diffusion barriers, and microstructural changes. Density functional theory-based molecular dynamics simulations indicate that oxygen diffusivity in BCC iron is 3.88 × 10 –5 cm 2 /s which is ∼5–10 times higher than that in FCC iron. This study reports that this stagnant reduction degree in the mixed solid–liquid phase is due to competition of multiple mechanisms, such as surface- and bulk-diffusion, pore collapse mechanisms, and crystallographic transitions.

08 HYDROGEN↗

Novel 1D coordination polymer {l_brace}Tm(Piv){sub 3{r_brace}n}: Synthesis, structure, magnetic properties and thermal behavior

The new 1D coordination polymer {l_brace}Tm(Piv){sub 3{r_brace}n} (1), where Piv=OOCBu{sup t-}, was synthesized in high yield (>95%) by the reaction of thulium acetate with pivalic acid in air at 100 Degree-Sign S. According to the X-ray diffraction data, the metal atoms in compound 1 are in an octahedral ligand environment unusual for lanthanides. The magnetic and luminescence properties of polymer 1, it's the solid-phase thermal decomposition in air and under argon, and the thermal behavior in the temperature range of -50 Horizontal-Ellipsis +50 Degree-Sign S were investigated. The vaporization process of complex 1 was studied by the Knudsen effusion method combined with mass-spectrometric analysis of the gas-phase composition in the temperature range of 570-680 K. - Graphical Abstract: Novel 1D coordination polymer {l_brace}Tm(Piv){sub 3{r_brace}n} was synthesized and studied by X-ray diffraction. The magnetic, luminescence properties, the thermal behavior and the volatility for the compound {l_brace}Tm(Piv){sub 3{r_brace}n} were investigated. Black-Small-Square Highlights: Black-Right-Pointing-Pointer We synthesized the coordination polymer {l_brace}Tm(Piv){sub 3{r_brace}n}. Black-Right-Pointing-Pointer Tm atoms in polymer have the coordination number 6. Black-Right-Pointing-Pointer Polymer exhibits blue-color emission at room temperature. Black-Right-Pointing-Pointer Polymer shows high thermal stability and volatility. Black-Right-Pointing-Pointer Polymer has no phase transitions in the range of -50 Horizontal-Ellipsis +50 Degree-Sign S.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗