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At least 1,153 records · Page 64

Engineering of flat bands and Dirac bands in two-dimensional covalent organic frameworks (COFs): relationships among molecular orbital symmetry, lattice symmetry, and electronic-structure characteristics

Two-dimensional covalent organic frameworks (2D-COFs), also referred to as 2D polymer networks, display unusual electronic-structure characteristics, which can significantly enrich and broaden the fields of electronics and spintronics. In this Focus article, the objective of this report is to lay the groundwork for the conceptual description of the fundamental relationships among the COF electronic structures, the symmetries of their 2D lattices, and the frontier molecular orbitals (MOs) of their core and linker components. We focus on monolayers of hexagonal COFs and use tight-binding model analyses to highlight the critical role of the frontier-MO symmetry, in addition to lattice symmetry, in determining the nature of the electronic bands near the Fermi level. We rationalize the intriguing feature that, when the core unit has degenerate highest occupied MOs [or lowest unoccupied MOs], the COF highest valence band [or lowest conduction band] is flat but degenerate with a dispersive band at a high-symmetry point of the Brillouin zone; the consequences of having such band characteristics are briefly described. Multi-layer and bulk 2D COFs are found to maintain the salient features of the monolayer electronic structures albeit with a reduced bandgap due to the interlayer coupling. This Focus article is thus meant to provide an effective framework for the engineering of flat and Dirac bands in 2D polymer networks.

36 MATERIALS SCIENCE↗

Understanding how chemical structure affects ignition-delay-time $\phi$-sensitivity

$\phi$-sensitivity is the change in ignition delay time (IDT) with respect to the fuel-to-air equivalence ratio ($\phi$). High $\phi$-sensitivity is a desirable fuel property for applications in advanced compression ignition and multi-mode engine designs. Understanding how $\phi$-sensitivity depends on chemical structure is essential for selecting promising biofuels from the ever-growing list of proposed candidates. Here, we investigate the effect of chemical structure on $\phi$-sensitivity with experiment, simulation, and theory. Experimental Advanced Fuel Ignition Delay Analyzer (AFIDA) measurements for 2,4-dimethylpentane and diisopropyl ether provide evidence that branching and functional groups strongly impact $\phi$-sensitivity. Further insights into this dependence are obtained with 0-D kinetic simulations with existing mechanisms for n-pentane, diethyl ether, 3-pentanone, n-heptane, 2-methylhexane, 2,4-dimethylpentane, and 2,2,3-trimethylbutane. Quantum mechanical (QM) G4 calculations of low-temperature reactions help explain the observed experimental and simulation trends. Specifically, these QM calculations provide theoretical estimates of the ketohydroperoxide (KHP) dissociation rates, the HO 2 formation rates from peroxy radical (ROO), and the “cross-over” temperatures, i.e., the temperature at which ROO dissociation is favored compared to hydroperoxyl radical (QOOH) formation. Each of these reaction rates is compared to the n-alkane reference point to determine the impact of branching and different functional groups. Although kinetic mechanisms typically assume that KHP dissociation rates are invariant of chemical environment, our QM results suggest that this rate can span a range of roughly two orders of magnitude. We also discuss the importance of including the peroxy-hydroperoxy (OO-OOH) hydrogen transfer reaction for branched ethers. Finally, the insights gained assist in proposing a highly $\phi$-sensitive compound, namely, isopropyl propyl ether.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface and grain boundary carbon heterogeneity in CH 3 NH 3 PbI 3 perovskites and its impact on optoelectronic properties

Rivaling state-of-the-art crystalline silicon, organic-inorganic hybrid perovskites have been intensely studied in recent years. Surface and interfacial engineering have been a focus for performance improvement. Even though significant progress has been made during the last decade in terms of the diversity and capability of perovskite-based devices, the structure-property relationship, particularly at the surface, which governs the real-world performance of these applications, is still unresolved. In the article, this issue was addressed by employing synchrotron-related experimental measurements, and a mechanism that correlates microstructure with surface chemistry was resolved. As a powerful and highly sensitive spectromicroscopy, soft x ray photoemission electron microscopy (X-PEEM) was used to probe the surface of perovskite films varying in post solvent annealing. Furthermore, static and in situ grazing incidence hard x ray diffraction (GIXD) was used to track the grain growth dynamics during the film formation process. It was found that the nature of the surfaces was dictated by the local chemistry that varied due to mass flow during the development of the microstructure. Combining optical and electronic characterizations, it was confirmed that a more homogenous chemistry, i.e., uniform chemical components and properties, along with reduced strain and grain boundary energies, yielded more defect-tolerant films. Grain boundaries were more favorable for screening carriers than those in the control film. Our findings underscore the importance of the uniformity in the surface for developing a chemistry-structure-property relationship in perovskite materials, as well as engineering local chemistry toward high-performance and stable devices.

42 ENGINEERING↗

The influence of cooling rates on strain phase diagrams and domain structures of ferroelectric thin films: A case study of PbTiO 3

Strain engineering has been established as an effective approach to control phase equilibria, domain configurations, and functional properties of ferroelectric thin films. Temperature-strain phase diagrams have been used as powerful tools for providing insights into strain engineering. However, almost all existing phase diagrams established using the phase-field approach assume quenching conditions without considering actual cooling rates during the post-deposition annealing process of ferroelectric thin films. Within this work, we systematically investigate the influence of cooling rates on domain structures and the strain-phase diagram of ferroelectric thin films using phase-field simulations, taking PbTiO 3 thin films as a model system. We found that both the position of phase boundaries in the strain phase diagrams and the domain morphology are significantly influenced by the cooling rates. It is revealed that while the paraelectric-ferroelectric phase boundary remains invariant, the phase boundaries between single-phase and multi-phase regions tend to shift toward the corresponding multi-phase region as the cool rate reduces. Slow cooling generally leads to more ordered domain structures with increased domain size. Using the obtained equilibrium domain structures, we calculated effective thermal conductivities and found significant variations that can be tuned by the cooling rates. In conclusion, this work reveals an underexplored yet critical impact of cooling rates on phase equilibria and domain structures in ferroelectric thin films, which may inspire further fine-tuning of domains and domain walls in low-dimensional ferroelectrics for multifunctional applications.

Domain structures↗

Ligand dynamics control structure, elasticity, and high-pressure behavior of nanoparticle superlattices

Precise engineering of nanoparticle superlattices (NPSLs) for energy applications requires a molecular-level understanding of the physical factors governing their morphology, periodicity, mechanics, and response to external stimuli. Such knowledge, particularly the impact of ligand dynamics on physical behavior of NPSLs, is still in its infancy. Here in this paper, we combine coarse-grained molecular dynamics simulations, and small angle X-ray scattering experiments in a diamond anvil cell to demonstrate that coverage density of capping ligands (i.e., number of ligands per unit area of a nanoparticle's surface), strongly influences the structure, elasticity, and high-pressure behavior of NPSLs using face-centered cubic PbS-NPSLs as a representative example. We demonstrate that ligand coverage density dictates (a) the extent of diffusion of ligands over NP surfaces, (b) spatial distribution of the ligands in the interstitial spaces between neighboring NPs, and (c) the fraction of ligands that interdigitate across different nanoparticles. We find that below a critical coverage density (1.8 nm-2 for 7 nm PbS NPs capped with oleic acid), NPSLs collapse to form disordered aggregates via sintering, even under ambient conditions. Above the threshold ligand coverage density, NPSLs surprisingly preserve their crystalline order even under high applied pressures (~40–55 GPa), and show a completely reversible pressure behavior. This opens the possibility of reversibly manipulating lattice spacing of NPSLs, and in turn, finely tuning their collective electronic, optical, thermo-mechanical, and magnetic properties.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Additive Engineering for Efficient and Stable Perovskite Solar Cells

Perovskite solar cells (PSCs) have reached a certified 25.2% efficiency in 2019 due to their high absorption coefficient, high carrier mobility, long diffusion length, and tunable direct bandgap. However, due to the nature of solution processing and rapid crystal growth of perovskite thin films, a variety of defects can form as a result of the precursor compositions and processing conditions. The use of additives can affect perovskite crystallization and film formation, defect passivation in the bulk and/or at the surface, as well as influence the interface tuning of structure and energetics. Here, recent progress in additive engineering during perovskite film formation is discussed according to the following common categories: Lewis acid (e.g., metal cations, fullerene derivatives), Lewis base based on the donor type (e.g., O-donor, S-donor, and N-donor), ammonium salts, low-dimensional perovskites, and ionic liquid. Various additive-assisted strategies for interface optimization are then summarized; additives include modifiers to improve electron- and hole-transport layers as well as those to modify perovskite surface properties. To conclude, an outlook is provided on research trends with respect to additive engineering in PSC development.

14 SOLAR ENERGY↗

Boosting Superior Lithium Storage Performance of Alloy-Based Anode Materials via Ultraconformal Sb Coating–Derived Favorable Solid-Electrolyte Interphase

Alloy materials such as Si and Ge are attractive as high-capacity anodes for rechargeable batteries, but such anodes undergo severe capacity degradation during discharge-charge processes. Compared to the over-emphasized efforts on the electrode structure design to mitigate the volume changes, understanding and engineering of the solid-electrolyte interphase (SEI) are significantly lacking. This work demonstrates that modifying the surface of alloy-based anode materials by building an ultraconformal layer of Sb can significantly enhance their structural and interfacial stability during cycling. Combined experimental and theoretical studies consistently reveal that the ultraconformal Sb layer is dynamically converted to Li 3 Sb during cycling, which can selectively adsorb and catalytically decompose electrolyte additives to form a robust, thin, and dense LiF-dominated SEI, and simultaneously restrain the decomposition of electrolyte solvents. Hence, the Sb-coated porous Ge electrode delivers much higher initial Coulombic efficiency of 85% and higher reversible capacity of 1046 mAh g -1 after 200 cycles at 500 mA g -1 , compared to only 72% and 170 mAh g -1 for bare porous Ge. The present finding has indicated that tailoring surface structures of electrode materials is an appealing approach to construct a robust SEI and achieve long-term cycling stability for alloy-based anode materials.

25 ENERGY STORAGE↗

Structure and Interactions of HIV-1 gp41 CHR-NHR Reverse Hairpin Constructs Reveal Molecular Determinants of Antiviral Activity

Engineered reverse hairpin constructs containing a partial C-heptad repeat (CHR) sequence followed by a short loop and full-length N-heptad repeat (NHR) were previously shown to form trimers in solution and to be nanomolar inhibitors of HIV-1 Env mediated fusion. Their target is the in situ gp41 fusion intermediate, and they have similar potency to other previously reported NHR trimers. However, their design implies that the NHR is partially covered by CHR, which would be expected to limit potency. An exposed hydrophobic pocket in the folded structure may be sufficient to confer the observed potency, or they may exist in a partially unfolded state exposing full length NHR. Here, in this study, we examined their structure by crystallography, CD and fluorescence, establishing that the proteins are folded hairpins both in crystal form and in solution. We examined unfolding in the milieu of the fusion reaction by conducting experiments in the presence of a membrane mimetic solvent and by engineering a disulfide bond into the structure to prevent partial unfolding. We further examined the role of the hydrophobic pocket, using a hairpin-small molecule adduct that occluded the pocket, as confirmed by X-ray footprinting. The results demonstrated that the NHR region nominally covered by CHR in the engineered constructs and the hydrophobic pocket region that is exposed by design were both essential for nanomolar potency and that interaction with membrane is likely to play a role in promoting the required inhibitor structure. The design concepts can be applied to other Class 1 viral fusion proteins.

59 BASIC BIOLOGICAL SCIENCES↗

Multi-Mode Cavity Accelerator Structure

This project aimed to develop a prototype for a novel accelerator structure comprising coupled cavities that are tuned to support modes with harmonically-related eigenfrequencies, with the goal of reaching an acceleration gradient >200 MeV/m and a breakdown rate <10 -7 /pulse/meter. Phase I involved computations, design, and preliminary engineering of a prototype multi-harmonic cavity accelerator structure; plus tests of a bimodal cavity. A computational procedure was used to design an optimized profile for a bimodal cavity with high shunt impedance and low surface fields to maximize the reduction in temperature rise ΔT. This cavity supports the TM010 mode and its 2nd harmonic TM011 mode. Its fundamental frequency is at 12 GHz, to benchmark against the empirical criteria proposed within the worldwide High Gradient collaboration for X-band copper structures; namely, a surface electric field E sur max < 260 MV/m and pulsed surface heating ΔT max < 56 °K. With optimized geometry, amplitude and relative phase of the two modes, reductions are found in surface pulsed heating, modified Poynting vector, and total RF power—as compared with operation at the same acceleration gradient using only the fundamental mode.

43 PARTICLE ACCELERATORS↗

Photoexcited Phenyl Ring Twisting in Quinodimethane Dyes Enhances Photovoltaic Performance in Dye-Sensitized Solar Cells

Four metal-free organic quinodimethane-based dyes, which represent molecular building blocks for a new class of DSSC dyes, were studied here with the objective to improve their photovoltaic performance via molecular engineering strategies. Such strategies can only be systematic and successful if they are derived from knowledge-based paradigms that relate individual aspects of the molecular structure for a given class of dyes to their photovoltaic properties. The optical and electrochemical properties of these dyes were investigated experimentally by UV–vis absorption and emission spectroscopy, as well as cyclic voltammetry and electrochemical impedance spectroscopy. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations on these dyes complement these experiments. Among other results, this concerted experimental and computational study revealed that the dialkylaminophenyl moiety in these dyes exhibits a large twist as a result of its ground-to-excited-state optical transition. In particular, a near-perpendicular (88.98°) twist of the dimethylaminophenyl moiety relative to the π-bridging unit that connects the three aryl rings in 2 was observed upon formation of its photo-excited-state structure. Moreover, it was discovered that 2 affords the highest V OC and power-conversion efficiency (PCE) values among these dyes. The particularly high PCE for 2 was found to be due to this twisting of the phenyl ring, which blocks the pathway of electrons from TiO 2 to the donor, and hence suppresses undesirable electron recombination at the dye···TiO 2 interface. This diode-like effect minimizes undesirable electron-recombination effects and represents an unprecedented structure–property relationship that should be useful for the molecular engineering of larger chromophores in this class of dyes for DSSC applications.

14 SOLAR ENERGY↗

Influence of isoelectronic mass modulation on phonon decay and transport in layered pnictogen-carbon systems

This study systematically investigates the structural, electronic, and thermal transport properties of layered pnictogen–carbon (Pn 2 C 2 ; Pn = P, As, Sb, Bi) monolayers, revealing a profound influence of isoelectronic mass modulation on phonon dynamics and thermal conductivity. Through first-principles calculations and lattice dynamics analysis, we demonstrate that increasing the atomic mass of pnictogens leads to elongated Pn-C bonds, weakened interatomic interactions, and enhanced phonon-phonon scattering, resulting in a dramatic reduction in lattice thermal conductivity (κ). Specifically, κ decreases exponentially from 65.6 W/m-K in P 2 C 2 to an ultralow 0.37 W/m-K in Bi 2 C 2 , driven by suppressed acoustic-optical phonon gaps Δ$^{Γ}_{A-0}$, increased anharmonicity, and reduced phonon lifetimes and group velocities. The transition from semiconducting to metallic behavior in heavier pnictogen-based systems further enhances phonon-electron scattering, contributing to thermal conductivity suppression. Structural analysis highlights the strengthening of out-of-plane C—C bonds and the contraction of C—Pn—C bond angles, which disrupt in-plane phonon transport. Further, these findings establish a design framework for engineering ultralow-κ materials through chemical substitution and structural tuning, offering significant potential for thermoelectric and thermal management applications. This work provides fundamental insights into phonon decay mechanisms and thermal transport in 2D materials, paving the way for advanced phononic and energy-efficient devices.

2D materials↗

Conceptual optimization using genetic algorithms for tube in tube structures

The purpose of this article is to optimize the tube in tube structural systems for tall buildings under the horizontal wind loads. It is well-known that the horizontal wind loads is the main criteria when choosing the structural system, the types and the dimensions of structural elements in the majority of tall buildings. Thus, the structural response of tall buildings under the horizontal wind loads will be analyzed for 40 story buildings and a total height of 120 meters; the horizontal dimensions will be 30m × 30m for the first two optimization problems and 15m × 15m for the third. The optimization problems will have the following as objective function the cross section area, as restrictions the displacement of the building< the admissible displacement (H/500), and as variables the cross section dimensions of the structural elements.

42 ENGINEERING↗

An Approach for Assessing Consequences of Potential Supply Chain and Insider Contributed Cyber Attacks on Nuclear Power Plants

The Stuxnet attack at the Natanz facility is an example of a targeted and successful cyber attack on a nuclear facility. Snowden's release of National Security Agency documents demonstrated the consequences of the insider threat. More recently, the United States tried to attack North Korea but failed, South Korea was attempting to attack North Korea, and both applied Stuxnet-like approaches. These sophisticated targeted attacks differ from web-site hacking events that are reported almost daily in the news mainly because targeted attacks require detailed design and operation information of the systems attacked and/or are often carried out by insiders. For instance, in order to minimize disruption of facilities around the world, Stuxnet remained idle until it recognized the specific configuration of the Natanz facility, demonstrating that the attackers possessed extremely detailed information about the facility. Such targeted cyber attacks could become a national-level military weapon and be used in coercion of hostile countries. While U.S. nuclear power plants (NPPs) are well designed and protected and not easily attacked through internet hacking, there have been a few digital-system-related incidents. For example, in 2003, the Slammer worm breached the private network of the Davis Besse plant and disabled a safety monitoring system for almost five hours. The breach did not pose a safety hazard because the plant was offline, but it demonstrates the vulnerability of NPP systems. The worm did not enter the plant systems directly; it began by entering the systems of a Davis Besse contractor, and entered through the T1 line bridging the contractor's computer and Davis Besse's corporate networks. The T1 line was not protected by the plant's firewall. The success of the Stuxnet-Natanz case demonstrates that supply-chain level attack (i.e., physically tampering with digital systems to install undetectable malware for the purpose of bringing harm to a player further down the supply chain network) plays a crucial role in a successful attack. Although attacking an NPP naturally requires more complex strategies and tactics than internet hacking, NPP's have a variety of sophisticated and possibly sensitive systems that may be attacked. Previous studies, for example, Baylon, have identified and confirmed that such attack strategies and tactics can be designed and could produce severe damage to an NPP. Current NPPs were designed according to design basis accidents that predate use of the internet by the general public and did not take into consideration potential cyber attacks that could be carried out by state-sponsored attackers and malicious insiders. To date, no detailed engineering analysis has been performed to realistically examine the consequences these attacks may have on the plants. In this paper, we discuss an approach for assessing the potential consequences of Stuxnet type of attacks. We will examine the engineering criteria used in designing the plants, develop possible attack scenarios in terms of the structures, components, and systems (SSCs) being controlled by digital systems at the NPPs, perform engineering analysis to determine if the attacks would impose conditions that are beyond design bases, and categorize the consequences of the potential accidents. (authors)

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Unveiling the structure and electronic characteristics of amorphous GeS for high performance threshold switching

Ovonic threshold switching selectors are widely studied owing to the essential application in high density phase-change memory. Amorphous GeS is proposed as a potential candidate for the excellent performance. However, the knowledge of amorphous GeS is still insufficient up to date. Here, we have studied the structure and electronic characteristics of GeS in the amorphization process, by using ab initio molecular dynamics simulations. The results indicate that the amorphous GeS is mainly made up of Ge–S bonds. The Ge- and S-centered clusters are dominantly in the form of octahedral structures in liquid GeS. Furthermore, during the amorphization process, most of Ge-centered clusters become highly coordinated octahedrons while a small number of Ge-centered clusters change to tetrahedrons, and the S-centered clusters deviate from the octahedral structure gradually. In addition, the large bandgap and the relatively small mid-gap states in amorphous GeS lead to a high switching voltage.

42 ENGINEERING↗

4D structural changes and pore network model of biomass during pyrolysis

Biochar is an engineered carbon-rich substance used for soil improvement, environmental management, and other diverse applications. To date, the understanding of how biomass affects biochar microstructure has been limited due to the complexity of analysis involved in tracing the changes in the physical structure of biomass as it undergoes thermochemical conversion. In this study, we used synchrotron x-ray micro-tomography to visualize changes in the internal structure of biochar from diverse feedstock (miscanthus straw pellets, wheat straw pellets, oilseed rape straw pellets, and rice husk) during pyrolysis by collecting a sequence of 3D scans at 50 °C intervals during progressive heating from 50 °C to 800 °C. The results show a strong dependence of biochar porosity on feedstock as well as pyrolysis temperature, with observed porosity in the range of 7.41–60.56%. Our results show that the porosity, total surface area, pore volume, and equivalent diameter of the largest pore increases with increasing pyrolysis temperature up to about 550 °C. The most dramatic development of pore structure occurred in the temperature range of 350–450 °C. This understanding is pivotal for optimizing biochar’s properties for specific applications in soil improvement, environmental management, and beyond. By elucidating the nuanced variations in biochar’s physical characteristics across different production temperatures and feedstocks, this research advances the practical application of biochar, offering significant benefits in agricultural, environmental, and engineering contexts.

54 ENVIRONMENTAL SCIENCES↗

Spectroscopy of Single AlInAs and (111)-Oriented InGaAs Quantum Dots

A system of AlInAs- and InGaAs(111)-based quantum dots is studied. The use of wide-gap Al{sub x}In{sub 1–x}As alloys as a basis for quantum dots provides a means for substantially extending the spectral region of emission to shorter wavelengths, including the region close to 770 nm which is of interest for the engineering of aerospace systems of quantum cryptography. The fine structure of exciton states in AlInAs and InGaAs(111) quantum dots is studied. It is shown that, for a set of quantum dots, the splitting of exciton states is comparable to the natural width of exciton lines, which is of interest for the engineering of emitters of photon pairs on the basis of these quantum dots.

36 MATERIALS SCIENCE↗

The Impact of Carbonation Curing on the Fatigue Behavior of Polyvinyl Alcohol Engineered Cementitious Composites (PVA-ECC)

Use of Engineered Cementitious Composites (ECC) has been proven to enhance structural fatigue resistance and reduce the use-phase emissions for transportation infrastructure. Carbonation curing offers an opportunity to reduce the embodied carbon of ECC via direct CO 2 sequestration. In this study, the impact of carbonation curing on ECC’s fatigue resistance was examined. ECC’s CO 2 uptake, static flexural behavior, flexural fatigue performance, and single fiber pull-out behavior were studied experimentally. Midspan deflection up to 3 million cycles under fatigue load, fatigue stress-life relationship, and failure mechanism for carbonation-cured and air-cured ECC were investigated. Carbonation curing was found to significantly improved the fatigue life of ECC and lowered the midspan deflection under the same stress. Further, CO 2 -cured ECC can achieve >20% CO 2 uptake per cement mass after 24-hour carbonation curing. Carbonation curing increased ECC’s flexural strength by 32% and promoted crack width control capability, with maximum post-fatigue crack width reduced from 148 μm to 76 μm. As a result, the positive impact of carbonation curing on the fatigue behavior of ECC simultaneously lowers the embodied and operational carbon of ECC structural members subjected to fatigue loading during service.

36 MATERIALS SCIENCE↗