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At least 1,603 records · Page 89

Is zero-point energy physical? A toy model for Casimir-like effect

Zero-point energy is generally known to be unphysical. Casimir effect, however, is often presented as a counterexample, giving rise to a conceptual confusion. To resolve the confusion we study foundational aspects of Casimir effect at a qualitative level, but also at a quantitative level within a simple toy model with only 3 degrees of freedom. In particular, we point out that Casimir vacuum is not a state without photons, and not a ground state for a Hamiltonian that can describe Casimir force. Instead, Casimir vacuum can be related to the photon vacuum by a non-trivial Bogoliubov transformation, and it is a ground state only for an effective Hamiltonian describing Casimir plates at a fixed distance. At the fundamental microscopic level, Casimir force is best viewed as a manifestation of van der Waals forces. - Highlights: • A toy model for Casimir-like effect with only 3 degrees of freedom is constructed. • Casimir vacuum can be related to the photon vacuum by a non-trivial Bogoliubov transformation. • Casimir vacuum is a ground state only for an effective Hamiltonian describing Casimir plates at a fixed distance. • At the fundamental microscopic level, Casimir force is best viewed as a manifestation of van der Waals forces.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Low-frequency and Moiré–Floquet engineering: A review

Highlights: • Review of theoretical and experimental advances in Floquet engineering. • Review of theories to derive effective Floquet Hamiltonians, with a focus on the low-frequency regime. • Review of the theoretical effects of light in Moiré materials. We review recent work on low-frequency Floquet engineering and its application to quantum materials driven by light, focusing on van der Waals systems hosting Moiré superlattices. These non-equilibrium systems combine the twist-angle sensitivity of the band structure with the flexibility of light drives. The frequency, amplitude, and polarization of light can be tuned in experimental setups, leading to platforms with on-demand properties. First, we review recent theoretical developments to derive effective Floquet Hamiltonians, emphasizing the low-frequency regime. We then review applications of some of these theories to study twisted graphene and transition metal dichalcogenide systems irradiated by light in free space and inside a waveguide. We study the changes induced in the quasienergies and steady-states, which can lead to topological transitions. Next, we consider van der Waals magnetic materials driven by low-frequency light pulses in resonance with the phonons. We discuss the phonon dynamics induced by the light and the resulting magnetic transitions from a Floquet perspective. We finish by outlining new directions for Moiré–Floquet engineering in the low-frequency regime and their relevance for technological applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Programmable intrusion detection for distributed energy resources in cyber–physical networked microgrids

We present a programmable intrusion detection method is presented to identify the malicious attacks to distributed energy resources (DERs) in the cyber-physical networked microgrids. The proposed method injects small programmable signals into the system and uses the response to identify abnormal conditions. Because of the low or even zero inertia induced by integrations of DER power-electronic-interfaces, microgrids have very limited resilience capability; and thus, being sensitive to attacks. One microgrid's malfunction caused by attacks can easily propagate to its neighboring systems when several microgrids are connected, leading to catastrophic electricity supply failures. Through the presented method, malicious intrusions can be effectively detected, located, and defended for securing microgrids. Theoretical derivations are provided to define the programmable detection rules. The detection rule is easy and flexible to update, making it difficult for attack actors to gain the knowledge of the detection rules, in order to avoid being detected. Numerical results on a cyber-physical networked microgrids system show that the proposed method is effective and efficient in precisely locating intrusion attacks to the microgrids system.

42 ENGINEERING↗

Molecular insights into the specific recognition between the RNA binding domain qRRM2 of hnRNP F and G-tract RNA: A molecular dynamics study

Heterogeneous nuclear ribonucleoprotein F (hnRNP F) controls the expression of various genes through regulating the alternative splicing of pre-mRNAs in the nucleus. It uses three quasi-RNA recognition motifs (qRRMs) to recognize G-tract RNA which contains at least three consecutive guanines. The structures containing qRRMs of hnRNP F in complex with G-tract RNA have been determined by nuclear magnetic resonance (NMR) spectroscopy, shedding light on the recognition mechanism of qRRMs with G-tract RNA. However, knowledge of the recognition details is still lacking. To investigate how qRRMs specifically bind with G-tract RNA and how the mutations of any guanine to an adenine in the G-tract affect the binding, molecular dynamics simulations with binding free energy analysis were performed based on the NMR structure of qRRM2 in complex with G-tract RNA. Simulation results demonstrate that qRRM2 binds strongly with G-tract RNA, but any mutation of the G-tract leads to a drastic reduction of the binding free energy. Further comparisons of the energetic components reveal that van der Waals and non-polar interactions play essential roles in the binding between qRRM2 and G-tract RNA, but the interactions are weakened by the effect of RNA mutations. Structural and dynamical analyses indicate that when qRRM2 binds with G-tract RNA, both qRRM2 and G-tract maintain stabilized structures and dynamics; however, the stability is disrupted by the mutations of the G-tract. These results provide novel insights into the recognition mechanism of qRRM2 with G-tract RNA that are not elucidated by the NMR technique. - Highlights: • qRRM2 has greater binding free energy with G-tract RNA than the mutated RNAs. • Non-polar and van der Waals interactions contribute mainly to the binding free energy. • qRRM2 maintains stabilized structure and dynamics when binding with G-tract RNA. • G-tract adopts stabilized conformation in complex with qRRM2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Binding orientation and interaction of bile salt in its ternary complex with pancreatic lipase-colipase system

Highlights: • Molecular dynamic simulation of porcine lipase-colipase with bile salt is performed. • Interactions between lipase-colipase and bile salt are analyzed. • Ternary complex is stabilized by van der Waals interactions. • Binding orientation of bile salt micelle on lipase-colipase is modelled. The interfacial activity of pancreatic lipases (PL) depends on the presence of colipase and bile salt. The activity of PL is inhibited by micellar concentrations of bile salt which can be restored by the addition of colipase. Though the formation of 1:1:1 tertiary complex by lipase-colipase-bile salt micelle is well accepted, the residue-level interactions between lipase-colipase and bile salt are yet to be clearly understood. Molecular dynamic simulations of lipase-colipase complex, lipase and colipase were performed in the presence of a model bile salt, sodium taurocholate (NaTC), at its near-CMC and supra-micellar concentrations. From the interactions obtained from the molecular dynamic simulations, the ternary complex was modelled and compared with earlier reports. The analysis suggested that a micelle of NaTC consisting of nine monomers was formed at the concave groove between lipase and colipase chain and it mainly interacted with the fourth finger of colipase. This complex was mainly stabilized by van der Waals interactions. Interestingly, the C-terminal domain of lipase which holds the colipase did not show any significant role in formation or stabilization of NaTC micelle.

60 APPLIED LIFE SCIENCES↗

Evaluating the Impact of Off-Design CHP Performance on the Optimal Sizing and Dispatch on Hybrid Renewable-CHP Distributed Energy Resources

The maturation of distributed energy resources (DER) has prompted the exploration of their deployment in commercial building applications due to their potential to supply energy at lower costs and emissions rates compared to centralized generation. While several software tools exist for evaluating the techno-economic potential of integrated renewable energy and combined heat and power (CHP) systems for distributed generation applications, many suffer from poor accuracy in capturing off-design (part load and changes in ambient air temperature and pressure) performance characteristics of microturbines, combustion turbines, or internal combustion engines. Thus, this paper presents a methodology for integrating these off-design characteristics in the mixed-integer linear program within REopt, a hybrid DER screening tool. The economic impact of the CHP off-design performance is observed through several application studies of various hybrid system configurations in different climates. Each study indicates how CHP off-design performance influences optimal sizing and dispatch decisions and therefore overall system economic value. We observe through case studies that modeling without the off-design effects, depending on the CHP prime mover and site, can result in Net Present Value predictions of hybrid systems that can be overoptimistic in frequently hot climates (up to 52%), too conservative in frequently cold climates (up to 11%), or unaffected (+/-1%) in temperate climates. Cases also highlight several advantages of hybrid systems relative to non-hybrid systems such as total economic value and the systems' ability to mitigate potentially negative consequences attributed to off-design performance.

ambient de-rate↗

Structural study of Ni- or Mg-based complexes incorporated within UiO-66-NH{sub 2} framework and their impact on hydrogen sorption properties

Nickel and magnesium acetylacetonate molecular complexes were post-synthetically incorporated into microporous zirconium-based MOF (UiO-66-NH{sub 2}) in order to introduce active open-metal sites for hydrogen sorption. Elemental analysis, nitrogen physisorption and DFT calculations revealed that 5 molecules of Ni(acac){sub 2} or 2 molecules of Mg(acac){sub 2} were incorporated into one unit cell of UiO-66-NH{sub 2}. {sup 1}H–{sup 13}C CPMAS and {sup 1}H MAS NMR spectroscopy showed that, although embedded within the pores, both Ni- and Mg-complexes interacted with the UiO-66-NH{sub 2} framework only through weak van der Waals bonds. Inclusion of metal complexes led to the decrease of hydrogen sorption capacities in Ni-modified as well as in Mg-modified samples in comparison with the parent UiO-66-NH{sub 2}. The isosteric hydrogen adsorption enthalpy slightly increased in the case of Ni-modified material, but not in the case of Mg-modified analogue. - Graphical abstract: A post-synthesis impregnation of Mg- and Ni-acetylacetonate complexes performed on zirconium-based MOF UiO-66-NH{sub 2} does influence the hydrogen sorption performance with respect to the parent matrix. The structural study revealed that Mg- and Ni-acetylacetonate molecules interact with zirconium-terephthalate framework only by weak interactions and they are not covalently bonded to aminoterephthalate ligand. Still, they remain confined into the pores even after hydrogen sorption experiments. - Highlights: • Mg- and Ni-acetylacetonate molecules embedded in the pores of UiO-66-NH{sub 2} by PSM. • Molecules of complexes interact with framework only by van der Waals interactions. • Type/structure of deposited metal-complex impact hydrogen enthalpy of adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Two supramolecular complexes based on polyoxometalates and Co-EDTA units via covalent connection or non-covalent interaction

Two new 3D network organic-inorganic hybrid supramolecular complexes ([Na{sub 6}(CoEDTA){sub 2}(H{sub 2}O){sub 13}]·(H{sub 2}SiW{sub 12}O{sub 40})·xH{sub 2}O)n (1) and [CoH{sub 4}EDTA(H{sub 2}O)]{sub 2}(SiW{sub 12}O{sub 40})·15H{sub 2}O (2) (H{sub 4}EDTA=Ethylenediamine tetraacetic acid) have been successfully synthesized by solution method, and characterized by infrared spectrum (IR), thermogravimetric-differential thermal analysis (TG-DTA), cyclic voltammetry (CV) and single{sup −}crystal X-ray diffraction (XRD). Both of the complexes are the supramolecules, but with different liking mode, they are two representative models of supramolecule. complex (1) is a 3D infinite network supramolecular coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through coordinate-covalent bonds. While complex (2) is normal supramolecule, which linked by non-covalent interactions, such as H-bonding interaction, electrostatic interaction and van der waals force. Both of complex (1) and (2) exhibit good catalytic activities for catalytic oxidation of methanol, when the initial concentration of methanol is 3.0 g m{sup −3}, flow rate is 10 mL min{sup −1}, and the quality of catalyst is 0.2 g, for complex (1) and complex (2) the maximum elimination rates of methanol are 85% (150 °C) and 92% (120 °C), respectively. - Graphical abstract: Two new organic-inorganic hybrid supramolecular complexes based on Co-EDTA, and Keggin polyanions have been successfully synthesized with different pH value by solution method. They are attributed to two representative models of supramolecule. Complex(1) is an infinite coordination polymer with a rare multi-metal sturcture of sodium-cobalt-containing, which is mainly linked through covalent bonds. Complex (2) is a normal supramolecule, which linked by non-covalent interactions of H-bonding interaction, electrostatic interaction and van der waals force. - Highlights: • Two supramolecules are linked by covalent or non-covalent interactions. • They are attributed to two representative models of supramolecule. • A rare multi-metal infinite supramolecular coordination polymer was formed. • They exhibit good catalytic activities for catalytic oxidation of methanol.

36 MATERIALS SCIENCE↗

Adsorption mechanism of alkyl polyglucoside (APG) on calcite nanoparticles in aqueous medium at varying pH

In this study, adsorption mechanism of alkyl polyglucoside (APG) on calcium carbonate (CaCO{sub 3}) nanoparticles (CCNPs) in aqueous medium at varying pH was identified. An initial adsorption of APG on CCNP surface seemed to be occurred due to the van der Waals force. An initial surface charge influenced determination of a major driving force, which resulted in hydrogen bonds (pH 7) and the hydrophobic interaction (pH 10) as a main sources of adsorption of APG on the CCNP surface. Even if the initial surface charge of CCNPs had little effect on a quantitative adsorption of APG on CCNPs, eventually, it influence on the definitive adsorption structure between APG and CCNPs and improvement of dispersion stability of CCNPs in water. In conclusion, it was revealed that 0.39% APG aqueous solution was most appropriate to improve the dispersion stability of CCNPs, which is postulated to be used effectively in food and pharmaceutical fields. - Graphical abstract: An initial adsorption of APG on CCNP surface seemed to be occurred due to the van der Waals force. An initial surface charge influenced determination of a major driving force, which resulted in hydrogen bonds (pH 7) and the hydrophobic interaction (pH 10) as a main sources of adsorption of APG on the CCNP surface. The difference in adsorption structure caused difference in improvement of dispersion stability of CCNPs in an aqueous medium. - Highlights: • The initial adsorption of APG on CCNPs occurs by a weak hydrophobic interaction. • At pH 7, the positively charged surface of CCNPs causes hydrogen bonds with APG. • At pH 7, the interfacial hydrogen bonds cause low stability of CCNPs in DI water. • At pH 10, zero charge of CCNPs causes a strong hydrophobic interaction with APG. • At pH 10, the hydrophobic interaction cause high stability of CCNPs in DI water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Few-layer tin sulfide (SnS): Controlled synthesis, thickness dependent vibrational properties, and ferroelectricity

Group IV monochalcogenides, anisotropic van der Waals crystals (and black phosphorus analogues), are attracting increasing interest due to a number of exceptional properties including anisotropic optoelectronics and multiferroicity predicted and in part realized in the ultrathin limit. Due to their enhanced chemical reactivity, both exfoliation and synthesis of monolayer and few-layer crystals pose challenges not found in other 2D/layered materials, such as the transition metal dichalcogenides. In this work, we show that SnS synthesis on SnS 2 van der Waals substrates can address these challenges and consistently produces few-layer flakes, a capability that is explained via analysis of real-time microscopy of the growth process. Raman spectroscopy combined with efficient computations of the Raman-active modes across an extended thickness range enables a comprehensive understanding of the evolution of the vibrational properties of SnS with number of layers. Lateral piezoresponse force microscopy provides unprecedented insight into the stacking-dependent polarization and ferroelectric domain structures in large few-layer SnS flakes. The combined results establish a basis for further fundamental studies and applications of SnS and other group IV monochalcogenides in the few-layer regime.

36 MATERIALS SCIENCE↗

Coherent Magnon–Photon Coupling in the Magnetic Semiconductor CrSBr

Magnon-based hybrid quantum systems are promising candidates for quantum interconnects and quantum sensors, and they offer a rich platform for exploring nonlinear magnonics and cavity–photon interactions. Two-dimensional (2D) van der Waals magnets provide a compact, atomically flat geometry that can be easily integrated into existing quantum circuits, such as superconducting resonators and qubits. Among various 2D magnets, the magnetic semiconductor CrSBr is particularly unique due to its strong spin–exciton, spin–lattice, and magnon–exciton interactions. In this work, we demonstrate coherent coupling between antiferromagnetic (AFM) magnons in CrSBr and microwave photons in a niobium-(Nb)-based-on-chip resonator. We tuned the magnon–photon coupling strength by changing the number of CrSBr flakes integrated into the Nb microwave photon resonators. Furthermore, this work demonstrates the first step toward integrating layered van der Waals 2D magnets into superconducting microwave circuits, with full access for microwave and optical probing.

Electromagnetic radiation↗

Valley Manipulation by Optically Tuning the Magnetic Proximity Effect in WSe 2 /CrI 3 Heterostructures

Monolayer valley semiconductors, such as tungsten diselenide (WSe 2 ), possess valley pseudospin degrees of freedom that are optically addressable but degenerate in energy. Lifting the energy degeneracy by breaking time-reversal symmetry is vital for valley manipulation. This has been realized by directly applying magnetic fields or via pseudomagnetic fields generated by intense circularly polarized optical pulses. However, sweeping large magnetic fields is impractical for devices, and the pseudomagnetic fields are only effective in the presence of ultrafast laser pulses. The recent rise of two-dimensional (2D) magnets unlocks new approaches to controlling valley physics via van der Waals heterostructure engineering. Here, we demonstrate the wide continuous tuning of the valley polarization and valley Zeeman splitting with small changes in the laser-excitation power in heterostructures formed by monolayer WSe 2 and 2D magnetic chromium triiodide (CrI 3 ). The valley manipulation is realized via the optical control of the CrI 3 magnetization, which tunes the magnetic exchange field over a range of 20 T. Lastly, our results reveal a convenient new path toward the optical control of valley pseudospins and van der Waals magnetic heterostructures.

2D magnets↗

Thickness-Dependent Interlayer Charge Transfer in MoSe 2 /MoS 2 Heterostructures Studied by Femtosecond Transient Absorption Measurements

We report observations of a strong thickness dependence for charge transfer (CT) from MoSe 2 to MoS 2 , as evidenced by transient absorption measurements. By time-resolving CT from MoSe 2 monolayers (1Ls) to MoS 2 flakes of varying thicknesses, including 1L, bilayer (2L), and trilayer (3L), we find that the CT time is several picoseconds in the 1L-MoSe 2 /3L-MoS 2 heterostructure, which is much longer than that of 1L-MoSe 2 /1L-MoS 2 and 1L-MoSe 2 /2L-MoS 2 heterostructures. In addition, the recombination lifetime of the interlayer excitons in the 1L/3L heterostructure is several times longer than that of 1L/1L and 1L/2L heterostructures, reaching 800 ps. Furthermore, we show that a prepulse can reduce the CT time and enhance the interlayer exciton recombination in the 1L/3L heterostructure. Furthermore, these findings illustrate that layer thickness can be an important parameter to control the CT property of van der Waals heterostructures. These experimental results also provide important information for further refining the understanding of the physical mechanisms of CT in van der Waals heterostructures.

36 MATERIALS SCIENCE↗

Tuning the Magnetic Properties of CrI 3 Using Ni Thin Film Deposition for Applications in Spintronic Devices

Chromium triiodide (CrI 3 ), a van der Waals magnet, has recently been shown to host Ising ferromagnetism down to the monolayer limit. It is a potentially important material in 2D magnet-based applications, such as magnetic sensors and spintronic devices. Prior studies have revealed the coexistence of two different types of interlayer magnetic coupling, the antiferromagnetic (AFM) coupling near the surface and ferromagnetic (FM) coupling in the deep bulk layers, in pristine CrI 3 crystals below the Curie temperature. In this study, we used Ni thin film deposition to tune the surface magnetic states in bulk CrI 3 . A nanometer thickness (4 nm thick) of Ni was deposited on the surface of CrI 3 using electron-beam evaporation to form a Ni/CrI 3 heterostructure. The deposited Ni thin layer forms nanoclusters that completely cover the CrI 3 surface. Magnetic states of CrI 3 before and after Ni deposition are probed by ultralow-frequency magneto-Raman spectroscopy. Instead of seeing three spin wave branches in Raman scattering below 2 T, as in pristine bulk CrI 3 , in Ni/CrI 3 , we observe only a single spin wave branch, which is softened compared to that in pristine CrI 3 and displays a Zeeman shift under an out-of-plane magnetic field up to 7 T. This observation reveals that the AFM layers on pristine CrI 3 crystal surfaces transit into FM layers, so the entire CrI 3 crystal is in the FM state after Ni deposition. First-principles calculations show that Ni atoms tend to diffuse into the CrI 3 lattice, and the FM interlayer coupling has a much lower energy than AFM coupling in the presence of Ni atoms. As a result, our studies show that the magnetic state of CrI 3 can be modified through deposition of a thin metal layer on the surface, offering a route for controlling the spin degree of freedom in van der Waals magnets.

36 MATERIALS SCIENCE↗

DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts

The adsorption of 20 nitrogen-/sulfur-containing and hydrocarbon compounds on the sulfur edge of cobalt-promoted molybdenum sulfide (CoMoS) catalyst was studied using density functional theory, accounting for van der Waals interactions, to elicit comparative structure–property trends across different classes of molecules relevant to hydrotreating. Unhindered organosulfur compounds preferentially adsorb on a “CUS-like” site formed by the dimerization of two neighboring sulfur atoms on the edge to create a vacancy. Nitrogen-containing compounds and 4,6-dimethyldibenzothiophene, however, prefer the brim sites. Binding energy trends indicate that nitrogen-containing compounds will inhibit hydrodesulfurization on the brim sites and, relatively weakly, on the CUS-like sites. Edge vacancies are,thus, likely to be essential for hydrodesulfurization of unhindered organosulfur compounds. Furthermore, van der Waals forces contribute significantly to the binding energy of compounds (up to 1.0 eV for large compounds such as alkyl-substituted acridines) on CoMoS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spatiotemporal Observation of Quasi-Ballistic Transport of Electrons in Graphene

We report spatiotemporal observations of room-temperature quasi-ballistic electron transport in graphene, which is achieved by utilizing a four-layer van der Waals heterostructure to generate free charge carriers. The heterostructure is formed by sandwiching a MoS 2 and MoSe 2 heterobilayer between two graphene monolayers. Transient absorption measurements reveal that the electrons and holes separated by the type-II interface between MoS 2 and MoSe 2 can transfer to the two graphene layers, respectively. Transient absorption microscopy measurements, with high spatial and temporal resolution, reveal that while the holes in one graphene layer undergo a classical diffusion process with a large diffusion coefficient of 65 cm 2 s –1 and a charge mobility of 5000 cm 2 V –1 s –1 , the electrons in the other graphene layer exhibit a quasi-ballistic transport feature, with a ballistic transport time of 20 ps and a speed of 22 km s –1 , respectively. The different in-plane transport properties confirm that electrons and holes move independently of each other as charge carriers. Furthermore, the optical generation of ballistic charge carriers suggests potential applications for such van der Waals heterostructures as optoelectronic materials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Anomalous Interlayer Exciton Diffusion in WS 2 /WSe 2 Moiré Heterostructure

Stacking van der Waals crystals allows for the on-demand creation of a periodic potential landscape to tailor the transport of quasiparticle excitations. We investigate the diffusion of photoexcited electron-hole pairs, or excitons, at the interface of WS 2 /WSe 2 van der Waals heterostructure over a wide range of temperatures. We observe the appearance of distinct interlayer excitons for parallel and antiparallel stacking and track their diffusion through spatially and temporally resolved photoluminescence spectroscopy from 30 to 250 K. While the measured exciton diffusivity decreases with temperature, it surprisingly plateaus below 90 K. Our observations cannot be explained by classical models like hopping in the moiré potential. A combination of ab initio theory and molecular dynamics simulations suggests that low-energy phonons arising from the mismatched lattices of moiré heterostructures, also known as phasons, play a key role in describing and understanding this anomalous behavior of exciton diffusion. Our observations indicate that the moiré potential landscape is dynamic down to very low temperatures and that the phason modes can enable efficient transport of energy in the form of excitons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗