The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter per...The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.展开更多
The effects of pressure on the structural stability,elasticity,electronic properties,and thermodynamic properties of Al,Al_(3)Cu,Al_(2)Cu,Al_(4)Cu_(9),AlCu_(3),and Cu were investigated using first-principles calculati...The effects of pressure on the structural stability,elasticity,electronic properties,and thermodynamic properties of Al,Al_(3)Cu,Al_(2)Cu,Al_(4)Cu_(9),AlCu_(3),and Cu were investigated using first-principles calculations.The experimental results indicate that the calculated equilibrium lattice constant,elastic constant,and elastic modulus agree with both theoretical and experimental data at 0 GPa.The Young's modulus,bulk modulus,and shear modulus increase with increasing pressure.The influence of pressure on mechanical properties is explained from a chemical bond perspective.By employing the quasi-harmonic approximation model of phonon calculation,the temperature and pressure dependence of thermodynamic parameters in the range of 0 to 800 K and 0 to 100 GPa are determined.The findings demonstrate that the thermal capacity and coefficient of thermal expansion increase with increasing temperature and decrease with increasing pressure.This study provides fundamental data and support for experimental investigations and further theoretical research on the properties of aluminum-copper intermetallic compounds.展开更多
The vacuum reactive wetting and brazing of Er_(2)Si_(2)O_(7)/MoSi_(2) coatings were investigated using a (CoFeNiCrMn)_(88)Nb_(12) high-entropy alloy (HEA) brazing filler. The microstructural evolution and wettability ...The vacuum reactive wetting and brazing of Er_(2)Si_(2)O_(7)/MoSi_(2) coatings were investigated using a (CoFeNiCrMn)_(88)Nb_(12) high-entropy alloy (HEA) brazing filler. The microstructural evolution and wettability of the HEA filler were analyzed, with particular attention to the surface energy, interfacial stability, and electronic properties of the HEA filler/rare earth silicate coating system, as determined by density functional theory (DFT). As Nb diffused into the interface and the ErNbO_(4) phase formed, the wetting angle gradually decreased to 23.12° The effective wetting and spreading of the HEA brazing filler on the rare earth silicate coating surface are strongly correlated with the formation of the ErNbO_(4) phase at the interface. Furthermore, DFT calculations reveal that the interfacial bonding energy between the BCC' and FCC' phases and the ErNbO_(4) phase, after the wetting reaction, is significantly higher than the bonding energy between the initial filler and Er_(2)Si_(2)O_(7). This finding suggests that the formation of the ErNbO_(4) phase improves the wetting and spreading behavior of the filler.展开更多
Control of hyperfine interaction strength of shallow donors in Si is one of the central issues in realizing Kane quantum computers.First-principles calculations on the hyperfine Stark shift of shallow donors are chall...Control of hyperfine interaction strength of shallow donors in Si is one of the central issues in realizing Kane quantum computers.First-principles calculations on the hyperfine Stark shift of shallow donors are challenging since large supercells are needed to accommodate the delocalized donor wave functions.In this work,we investigated the hyperfine Stark shift and its strain tunability for shallow donors P and As in Si using the potential patching method based on first-principles density functional theory calculations.The good agreement between our calculations and experimental results confirms that the potential patching method is a feasible and accurate first-principles approach for studying wave-function-related properties of shallow impurities,such as the Stark shift parameter.It is further shown that the application of strain expands the range of hyperfine Stark shift and helps improve the response of shallow donor based qubit gates.The results could be useful for developing quantum computing architectures based on shallow donors in Si.展开更多
Understanding the adsorption behavior of heavy metals and metalloids on clay minerals is essential for remediating heavy metal-contaminated soils.The adsorption of heavy metals and metalloids on illite(001)and sodium ...Understanding the adsorption behavior of heavy metals and metalloids on clay minerals is essential for remediating heavy metal-contaminated soils.The adsorption of heavy metals and metalloids on illite(001)and sodium montmorillonite(Na-MMT)(001)surfaces was investigated using first-principles calculations in this study,especially As atom and H_(3)AsO_(3) molecule.The adsorption energies of the As atom were−1.94 eV on the illite(001)and−0.56 eV on the Na-MMT(001),whereas,the adsorption energies of the H_(3)AsO_(3) molecule were−1.40 eV on illite(001)and−1.01 eV on Na-MMT(001).The above results indicate that the adsorption was more energetically favorable on illite(001).Additionally,compared to Na-MMT(001),there were more significant interactions between the atoms/molecules on the illite(001).After As atom and H_(3)AsO_(3) molecule adsorption,the electrons were transferred from mineral surface atoms to the adsorbates on both illite(001)and Na-MMT(001)surfaces.Moreover,the adsorption of As atom on illite(001)and Na-MMT(001)surfaces were more energy favorable compared to Hg,Cd,and Cr atoms.Overall,this work provides new insights into the adsorption behavior of As atoms and As molecules on illite and Na-MMT.The results indicate that illite rich soils are more prone to contamination by arsenic compared to soils primarily composed of Na-MMT minerals.展开更多
Ni-Mn-Ti Heusler alloys have great potential for elastocaloric refrigeration due to the colossal caloric effect and good mechanical properties. However, theoretical calculations on the characterization of the elastoca...Ni-Mn-Ti Heusler alloys have great potential for elastocaloric refrigeration due to the colossal caloric effect and good mechanical properties. However, theoretical calculations on the characterization of the elastocaloric effect are rare. An important parameter to evaluate the elastocaloric effect is the transformation entropy change, whose main source is the vibrational entropy change (ΔS_(vib)). Unfortunately, the widely used quasiharmonic approximation method fails in the prediction of the vibrational entropy for high-temperature austenite due to its dynamical instability at 0 K. To solve this problem, the temperature dependent effective potential method was used considering the temperature and anharmonic effect. Sc, V, and Zr doping at the Ti sites in B2 disordered Ni_(8)Mn_(5)Ti_(3) were studied about phase stability, martensitic transformation, and elastocaloric properties. The results revealed the austenitic structures of all the doping systems exhibit antiferromagnetic coupling characteristics at 300 K due to the temperature effect. Sc and Zr doping at the Ti sites decreased the ΔS_(vib) value, whereas V doping at the Ti site increased the ΔS_(vib) value. Further analysis proved the important evaluation criterion that the ΔS_(vib) value increases with the tetragonal distortion ratio and volume change, which has important guiding significance for improving the elastocaloric effect. Besides, the calculations of elastic constants presented all the doping systems maintain outstanding ductility evaluated from the B/G ratio. This work provides an effective strategy for designing excellent elastocaloric material with large vibrational entropy change and good mechanical properties.展开更多
Neutron-rich boron,carbon,and nitrogen isotopes have garnered extensive experimental and theoretical interest.In the present work,we conducted a comprehensive study of these nuclei by utilizing ab initio valence-space...Neutron-rich boron,carbon,and nitrogen isotopes have garnered extensive experimental and theoretical interest.In the present work,we conducted a comprehensive study of these nuclei by utilizing ab initio valence-space in-medium similarity renormalization group calculations with chiral nucleon-nucleon and three-nucleon interactions.First,we systematically calculated the spectra of nuclei.Our results align well with the available experimental data,which are comparable to phenomenological shell model calculations.Subsequently,the evolution of the N=14 and N=16 shell gaps is discussed based on the calculated spectra and the effective single-particle energies.Our calculations suggest that the N=14 neutron subshell is present in the oxygen isotopes but disappears in the boron,carbon,and nitrogen isotopic chains.Moreover,the N=16 subshell is present in all isotopes but gradually decreases from^(24)O to^(21)B.These results provide valuable information for future studies.展开更多
Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers,dauroxonanols A(1)and B(2),possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.0^(4.17).0^(14.18)]octadecane core skeleton,were isolated from R...Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers,dauroxonanols A(1)and B(2),possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.0^(4.17).0^(14.18)]octadecane core skeleton,were isolated from Rhododendron dauricum.The nuclear magnetic resonance(NMR)spectra of 1 and 2 showed very broad resonances,and^(13)C NMR spectrum of 1 exhibited only 13 instead of 22 carbon resonances.These broadening or missing NMR resonances led to a great challenge to elucidate their structures using NMR data analysis.Their structures and absolute configurations of 1 and 2 were finally determined by single crystal X-ray diffraction analysis,chiral separation,and electronic circular dichroism(ECD)calculations.Plausible biosynthetic pathways for 1 and 2 are proposed.Conformational analysis,density functional theory(DFT)calculations,and dynamic NMR assigned the coalescent NMR phenomena of 1 and 2 to the conformational changes of the flexible oxonane ring.Dauroxonanols A(1)and B(2)showed potentα-glucosidase inhibitory activities,2-8 times potent than acarbose,an antidiabetic drug targetingα-glucosidase in clinic.展开更多
This study investigates the application of Gurney and flight of fragment equations,typically used to predict metal fragment velocities,in modeling the water jet behavior.Three shotgun cartridge sizes were used as the ...This study investigates the application of Gurney and flight of fragment equations,typically used to predict metal fragment velocities,in modeling the water jet behavior.Three shotgun cartridge sizes were used as the energy source:2.59 g,5.83 g,and 7.13 g.Two configurations were tested:standard(full-barrel water load)and"negative 8"(partial water load).High-speed footage captured water column velocities,and Gurney models,including infinitely tamped and open-faced configurations,combined with the flight of fragment model were used to assess prediction accuracy.Results showed charge strength significantly affects water column velocity,with higher strengths yielding greater stability and velocity retention over distance.The infinitely tamped Gurney model closely predicted experimental velocities,deviating by as little as 1.4%for standard charges and 2.8% for negative 8 charges.Additionally,interesting dynamics such as a 1-2°rise in jet height and the rear overtaking the front was observed.These findings have significant implications for optimizing PAN disruptors and enhancing performance in high-velocity fluid applications and explosive breaching systems.展开更多
To explain the influence mechanism of MgO on the consolidation and reduction characteristics of roasted iron pellets,the properties and structure of pellets were investigated from multi-dimensions.It indicated that th...To explain the influence mechanism of MgO on the consolidation and reduction characteristics of roasted iron pellets,the properties and structure of pellets were investigated from multi-dimensions.It indicated that the MgO addition decreased the reduction swelling index(RSI)and reduction degree of pellets in both CO and H_(2)atmospheres.During the stepwise reduction process of Fe2O3→Fe3O4→FeO,the reduction behaviour of pellets in CO and H_(2)was similar,while the reduction rate of pellets in H_(2)atmosphere was almost twice as high as that in CO atmosphere.During the stepwise reduction process of FeO→Fe,the RSI of pellets showed a logarithmic increase in CO atmosphere and a linear decrease in H_(2)atmosphere.As investigated by first-principles calculations,C and Fe mainly formed chemical bonds,and the CO reduction process released energy,promoting the formation of iron whiskers.However,H and Fe produced weak physical adsorption,and the H_(2)reduction process was endothermic,inhibiting the generation of iron whiskers.With Mg2+doping in FexO,the nucleation region of iron whiskers expanded in CO reduction process,and the morphology of iron whiskers transformed from“slender”to“stocky,”reducing RSI of the pellets.展开更多
High multipole electromagnetic transitions are rare in nature.The highest-multipole transition observed in atomic nuclei is the electric hexacontatetrapole E6 transition from the T_(1/2)=2.54(2)-min J^(π)=1_(9/2)-iso...High multipole electromagnetic transitions are rare in nature.The highest-multipole transition observed in atomic nuclei is the electric hexacontatetrapole E6 transition from the T_(1/2)=2.54(2)-min J^(π)=1_(9/2)-isomer to the 7/2^(-)ground state in^(53)Fe with an angular momentum change of six units.In the present work,we performed ab initio calculations for this unique case by employing chiral effective field theory(EFT)forces.The in-medium similarity renormalization group is used to derive the valence-space effective Hamiltonian and multipolar transition operators.Bare nucleon charges were used in all the multipolar transition rate calculations,providing good agreement with the experimental data.The valence space takes the full fp shell.In^(53)Fe,the low-lying states were dominated by the 0f_(7/2)component.Two different versions of the chiral EFT two-plus three-nucleon interaction were used to test the dependence on the interaction used.We also tested the convergence of the transition rate calculations against the harmonic oscillator parameter hΩand basis truncations e_(max)and E_(3max)for twoand three-nucleon forces,respectively.展开更多
Currently,the development of high-efficiency two-dimensional(2D)transistors is still hindered by the limited availability of suitable semiconductors and the contact resistance between the metal contact and the 2D semi...Currently,the development of high-efficiency two-dimensional(2D)transistors is still hindered by the limited availability of suitable semiconductors and the contact resistance between the metal contact and the 2D semiconductors.Endeavors to address these challenges are highly desired.In this study,we conducted a comprehensive exploration of the potential 2D transition metal dinitrides(TMN_(2)s,TM=all the 3d,4d and 5d transition metals)with hexagonal(h-)and trigonal(t-)phases through systematic first-principles calculations.Among all h-TMN_(2)s and t-TMN_(2)s structures,we identified 8 TMN_(2)s that exhibit dynamical and thermal stability at room temperature.Of these,the h-TiN_(2),h-ZrN_(2)and h-HfN_(2)arefound to be semiconductors,and their direct bang gap,calculated at the HSE06 level,are 1.48,1.96 and 2.64 eV,respectively.The electron and hole mobility(μ_(e)andμ_(h))of these three structures exceed 1×10^(4)and1×10^(3)cm^(2)·V^(-1)·s^(-1),respectively.Especially,theμeof h-TiN_(2)amounts to 2.5×10^(4)cm^(2)·V^(-1)·s^(-1),and theμhof h-ZrN_(2)reaches to 7.7×10^(3)cm^(2)·V^(-1)·s^(-1).Importantly,unlike the MoS_(2)system,h-TMN_(2)forms Ohm contacts with both transition metals(e.g.,Cu)and 2D metals(e.g.,graphene),with tunneling possibilities exceeding 50%in the Cu system.These outstanding intrinsic semiconductor properties and contact characteristics exhibited by h-TMN_(2)highlight the immense potential of transition metal dinitrides in driving the advancement of next-generation information devices.Our findings significantly broaden the range of 2D materials and provide valuable insights for the development of high-eficiency 2D information devices.展开更多
Magnets exhibiting the Kitaev interaction,a bond-dependent magnetic interaction in honeycomb lattices,are generally regarded as promising candidates for hosting novel phenomena like quantum spin liquid states.However,...Magnets exhibiting the Kitaev interaction,a bond-dependent magnetic interaction in honeycomb lattices,are generally regarded as promising candidates for hosting novel phenomena like quantum spin liquid states.However,realizing such magnets remains a significant challenge.Recently,some studies have suggested honeycomb magnets A_(3)Ni_(2)XO_(6)(A=Li,Na;X=Bi,Sb)with a high spin S=1 could serve as potential candidates for realizing strong Kitaev interactions.In this work,we systematically investigate their magnetic properties,with a particular emphasis on their Kitaev interactions,using first-principles calculations and Monte Carlo simulations.Our results indicate that all A_(3)Ni_(2)XO_(6)compounds are zigzag antiferromagnets,and their magnetic moments almost tend to be out of plane.We find that their dominant magnetic interactions are the nearest-neighbor ferromagnetic and third-nearest-neighbor antiferromagnetic Heisenberg interactions,while their Kitaev interactions are extremely weak.By analyzing their electronic structures and the mechanism of generating their magnetic interactions,we reveal that either artificially tuning spin-orbit coupling or applying strain cannot produce sufficient spin-orbit entangled states to realize the intriguing Kitaev interactions.Our work advances the understanding of the magnetism in A_(3)Ni_(2)XO_(6)compounds and provides insights for further exploration of Kitaev physics in honeycomb magnets.展开更多
In this paper, cold simulation experiments and numerical calculations are conducted to predict 3 D flow field aerodynamics for an oil furnace after being retrofitted due to its fuel variation. K ε model and SIMPLE ...In this paper, cold simulation experiments and numerical calculations are conducted to predict 3 D flow field aerodynamics for an oil furnace after being retrofitted due to its fuel variation. K ε model and SIMPLE program under body fit coordination (BFC) system, in which TTM non orthogonal method is used to control the irregular geometric boundary, are adopted to solve the control equations. Model tests are conducted to check the calculation results, showing that they are in agreement with each other. Three different alternatives with different side window locations are also calculated to optimize the designs. The field retrofitting results show that the combination of cold tests with numerical calculations has prosperous application in retrofitting or renewing medium and small boilers.展开更多
We investigated the structural evolution and elecfronic properties of ConC3-/0 and ConC4-/0 （n=1-4） clusters by using mass-selected photoelectron spectroscopy and density functional theory calculations. The adiabati...We investigated the structural evolution and elecfronic properties of ConC3-/0 and ConC4-/0 （n=1-4） clusters by using mass-selected photoelectron spectroscopy and density functional theory calculations. The adiabatic and vertical detachment energies of CO1-4C3- and COl-4C4- were obtained from their photoelectron spectra. By comparing the theoretical results with the experimental data, the global minimum structures were determined. The results indicate that the carbon atoms of ConC3-/0 and ConC4-/0 （n=1-4） are separated from each other gradually with increasing number of cobalt atoms but a C2 unit still remains at n=4. It is interesting that the Co2C3- and Co2C4- anions have planar structures whereas the neutral Co2C3 and Co2C4 have linear structures with the Co atoms at two ends. The Co3C3- anion has a planar structure with a Co2C2 four-membered ring and a Co3C four-membered ring sharing a Co-Co bond, while the neutral Co3C3 is a three-dimensional structure with a C2 unit and a C atom connecting to two faces of the Co3 triangle.展开更多
Two-phase equilibria between the ferromagnetic fcc and the paramagnetic fcc phase from 800 ℃ to 900 ℃ in the Co-rich region have been detected by the diffusion couple technique. Two phase separation region of the fc...Two-phase equilibria between the ferromagnetic fcc and the paramagnetic fcc phase from 800 ℃ to 900 ℃ in the Co-rich region have been detected by the diffusion couple technique. Two phase separation region of the fcc has been confirmed along the Curie temperature.The phase equilibria including the present results and the thermodynamic data of the Co-Cr system reported in the literature were analyzed on the basis of the thermodynamic evaluation. A set of thermodynamic values for the liquid, fcc, hcp, bcc, sigma phases was obtained. The calculated phase equilibria were in good agreement with most of the experimental data.展开更多
GeoPyTool is an open source application developed for geological calculations and plots,such as geochemical classification,parameter calculation,basic statistical analysis and diagrams for structural geology.More than...GeoPyTool is an open source application developed for geological calculations and plots,such as geochemical classification,parameter calculation,basic statistical analysis and diagrams for structural geology.More than acting as a link from raw data stored in Microsoft Excel■(MS Excel)files to vector graphic files,GeoPyTool includes recently developed routines that have not been included in previous software,such as the calculation of the Ce(Ⅳ)/Ce(Ⅲ)ratio for zircons as a method to examine the temporal evolution of oxygen fugacity in the magmatic source for igneous rocks,and the temperature calculator with titanium in zircon and zirconium in rutile.Besides these routines,GeoPyTool also allows users to load any figure from articles or books as a base map.As a Python-based crossplatform program,GeoPyTool works on Windows?,MacOS X?and GNU/Linux.GeoPyTool can do the whole process from data to results without the dependence of Microsoft Excel?,CorelDraw?and other similar software.It takes Excel?XLSX and CSV(Comma Separated Value)as the formats of both the input data source files and the output calculation results files.The figures generated by GeoPyTool can be saved as portable network graphics(PNG),scalable vector graphics(SVG)or portable document format(PDF).Another highlight of GeoPyTool is the multilingual support,the official versio n of GeoPyTool supports both Chinese and English,and additional languages can be loaded through interface files.GeoPyTool is still in the development stage and will be expanded with further geochemical and structural geology routines.As an open source project,all source code of GeoPyTool are accessible on Github(https://github.com/GeoPyTool/GeoPyTool).Users with Python experience can join in the development team and build more complex functions expanding the capabilities of GeoPyTool.展开更多
Three dimensional diagnostic,semidiagnostic and prognostic models in the σ coordinate are used to compute the current in the East China Sea with wind and hydrographic data obtained from the investigation of ocea...Three dimensional diagnostic,semidiagnostic and prognostic models in the σ coordinate are used to compute the current in the East China Sea with wind and hydrographic data obtained from the investigation of ocean fluxes in the East China Sea during the cruise of April 1994.The computed results show that:the density and velocity fields and so on have been adjusted when time t ≈ 23 d, i.e.,the solution of semidiagnostic calculation has been obtained.The quasi steady state solution also has been reached after about 60 d.Comparing the results of diagnostic calculation with those of semidiagnostic and prognostic calculations,it is found that they agree qualitatively.For example,they all show that:(1)The Kuroshio flows along the shelf break of 200～1 000 m isobaths;(2)In the southeastern part of the computational region there is a stronger counter current with an anticyclonic eddy;(3)The volume transport through Section PN is about 30×10 6m 3/s and so on.However there are some quantitative differences between them.For example,(1)For the semidiagnostic results the Kuroshio current is stronger and clearer than that for diagnostic results and the Kuroshio width is more narrow than that for diagnostic results.This shows that the semidiagnostic calculation can better reflect the topography effect;(2)In most computed region the vertical component of velocity intensifies for semidiagnostic result,especially on the shelf break.Comparing the results of semidiagnostic calculation with those of prognostic calculation,they agree qualitatively,and also agree quantitatively in the middle of computed region.展开更多
The physical characters and electrochemical properties of various phases in a Sn-Zn electrode, such as formation energy, plateau potential, specific capacity, as well as volume expansion, were calculated by the first-...The physical characters and electrochemical properties of various phases in a Sn-Zn electrode, such as formation energy, plateau potential, specific capacity, as well as volume expansion, were calculated by the first-principles plane-wave pseudo-potential method based on the den- sity functional theory. Sn-Zn films were also deposited on copper foils by an electroless plating technique. The actual composition and chemical characters were explored by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, plasma atomic emission spectrometry （ICP）, and constant current charge/discharge measurements （CC）. The results show that separation phases with tin and zinc including a small quantity of Cu6Sn5 phase were obtained, the initial lithium insertion capacity of the Sn-Zn film was 661 mAh/g, and obvious potential pla- teaus of about 0.4 V and 0.7 V were displayed, which is in accordance with the results of theoretical calculations. The capacity of the Sn-Zn film decreased seriously with the increase of cycle number.展开更多
The electronic structures of CuS2, CuSe2 and CuTe2 with pyrite structures, within the framework the density-functional theory have been investigated. The calculated results explained the recent experimental results wh...The electronic structures of CuS2, CuSe2 and CuTe2 with pyrite structures, within the framework the density-functional theory have been investigated. The calculated results explained the recent experimental results which show that there is no clear indication of strong electron correlations in the electronic properties of Cu pyrites, due to the dominant chalcogen p character rather than d characteristic of Cu at the Fermi level.展开更多
基金supported by the National Natural Science Foundation of China(52471240)the Natural Science Foundation of Zhejiang Province(LZ23B030003)+2 种基金the Fundamental Research Funds for the Central Universities(226-2024-00075)support from the Engineering and Physical Sciences Research Council(EPSRC,UK)RiR grant-RIR18221018-1EU COST CA23155。
文摘The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.
基金Funded by the National Key R&D Program of China(No.2021YFB3802300)the Foundation of National Key Laboratory of Shock Wave and Detonation Physics(No.JCKYS2022212004)the National Natural Science Foundation of China(No.52171045),and the Joint Fund(No.8091B022108)。
文摘The effects of pressure on the structural stability,elasticity,electronic properties,and thermodynamic properties of Al,Al_(3)Cu,Al_(2)Cu,Al_(4)Cu_(9),AlCu_(3),and Cu were investigated using first-principles calculations.The experimental results indicate that the calculated equilibrium lattice constant,elastic constant,and elastic modulus agree with both theoretical and experimental data at 0 GPa.The Young's modulus,bulk modulus,and shear modulus increase with increasing pressure.The influence of pressure on mechanical properties is explained from a chemical bond perspective.By employing the quasi-harmonic approximation model of phonon calculation,the temperature and pressure dependence of thermodynamic parameters in the range of 0 to 800 K and 0 to 100 GPa are determined.The findings demonstrate that the thermal capacity and coefficient of thermal expansion increase with increasing temperature and decrease with increasing pressure.This study provides fundamental data and support for experimental investigations and further theoretical research on the properties of aluminum-copper intermetallic compounds.
基金support from the National Natural Science Foundation of China(No.52374402)the National Key Research and Development Program(No.2022YFB3402200)+2 种基金the National Science and Technology Major Project(No.J2022-VII-0003-0045)the Project of Key areas of innovation team in Shaanxi Province(No.2024RS-CXTD-20)the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University(No.CX2024055).
文摘The vacuum reactive wetting and brazing of Er_(2)Si_(2)O_(7)/MoSi_(2) coatings were investigated using a (CoFeNiCrMn)_(88)Nb_(12) high-entropy alloy (HEA) brazing filler. The microstructural evolution and wettability of the HEA filler were analyzed, with particular attention to the surface energy, interfacial stability, and electronic properties of the HEA filler/rare earth silicate coating system, as determined by density functional theory (DFT). As Nb diffused into the interface and the ErNbO_(4) phase formed, the wetting angle gradually decreased to 23.12° The effective wetting and spreading of the HEA brazing filler on the rare earth silicate coating surface are strongly correlated with the formation of the ErNbO_(4) phase at the interface. Furthermore, DFT calculations reveal that the interfacial bonding energy between the BCC' and FCC' phases and the ErNbO_(4) phase, after the wetting reaction, is significantly higher than the bonding energy between the initial filler and Er_(2)Si_(2)O_(7). This finding suggests that the formation of the ErNbO_(4) phase improves the wetting and spreading behavior of the filler.
基金supported by the National Natural Science Foun-dation of China(Grant Nos.12393831 and 12088101).
文摘Control of hyperfine interaction strength of shallow donors in Si is one of the central issues in realizing Kane quantum computers.First-principles calculations on the hyperfine Stark shift of shallow donors are challenging since large supercells are needed to accommodate the delocalized donor wave functions.In this work,we investigated the hyperfine Stark shift and its strain tunability for shallow donors P and As in Si using the potential patching method based on first-principles density functional theory calculations.The good agreement between our calculations and experimental results confirms that the potential patching method is a feasible and accurate first-principles approach for studying wave-function-related properties of shallow impurities,such as the Stark shift parameter.It is further shown that the application of strain expands the range of hyperfine Stark shift and helps improve the response of shallow donor based qubit gates.The results could be useful for developing quantum computing architectures based on shallow donors in Si.
基金Project(22376221)supported by the National Natural Science Foundation of ChinaProject(2024JJ2074)supported by the Natural Science Foundation of Hunan Province,ChinaProject(2023QNRC001)supported by the Young Elite Scientists Sponsorship Program by CAST。
文摘Understanding the adsorption behavior of heavy metals and metalloids on clay minerals is essential for remediating heavy metal-contaminated soils.The adsorption of heavy metals and metalloids on illite(001)and sodium montmorillonite(Na-MMT)(001)surfaces was investigated using first-principles calculations in this study,especially As atom and H_(3)AsO_(3) molecule.The adsorption energies of the As atom were−1.94 eV on the illite(001)and−0.56 eV on the Na-MMT(001),whereas,the adsorption energies of the H_(3)AsO_(3) molecule were−1.40 eV on illite(001)and−1.01 eV on Na-MMT(001).The above results indicate that the adsorption was more energetically favorable on illite(001).Additionally,compared to Na-MMT(001),there were more significant interactions between the atoms/molecules on the illite(001).After As atom and H_(3)AsO_(3) molecule adsorption,the electrons were transferred from mineral surface atoms to the adsorbates on both illite(001)and Na-MMT(001)surfaces.Moreover,the adsorption of As atom on illite(001)and Na-MMT(001)surfaces were more energy favorable compared to Hg,Cd,and Cr atoms.Overall,this work provides new insights into the adsorption behavior of As atoms and As molecules on illite and Na-MMT.The results indicate that illite rich soils are more prone to contamination by arsenic compared to soils primarily composed of Na-MMT minerals.
基金supported by the National Natural Science Foundation of China(Nos.52271172,and 51971085).
文摘Ni-Mn-Ti Heusler alloys have great potential for elastocaloric refrigeration due to the colossal caloric effect and good mechanical properties. However, theoretical calculations on the characterization of the elastocaloric effect are rare. An important parameter to evaluate the elastocaloric effect is the transformation entropy change, whose main source is the vibrational entropy change (ΔS_(vib)). Unfortunately, the widely used quasiharmonic approximation method fails in the prediction of the vibrational entropy for high-temperature austenite due to its dynamical instability at 0 K. To solve this problem, the temperature dependent effective potential method was used considering the temperature and anharmonic effect. Sc, V, and Zr doping at the Ti sites in B2 disordered Ni_(8)Mn_(5)Ti_(3) were studied about phase stability, martensitic transformation, and elastocaloric properties. The results revealed the austenitic structures of all the doping systems exhibit antiferromagnetic coupling characteristics at 300 K due to the temperature effect. Sc and Zr doping at the Ti sites decreased the ΔS_(vib) value, whereas V doping at the Ti site increased the ΔS_(vib) value. Further analysis proved the important evaluation criterion that the ΔS_(vib) value increases with the tetragonal distortion ratio and volume change, which has important guiding significance for improving the elastocaloric effect. Besides, the calculations of elastic constants presented all the doping systems maintain outstanding ductility evaluated from the B/G ratio. This work provides an effective strategy for designing excellent elastocaloric material with large vibrational entropy change and good mechanical properties.
基金supported by the National Key R&D Program of China(Nos.2024YFE0109800 and 2024YFE0109802)the National Natural Science Foundation of China(Nos.12405141,12347106,12205340,and 12121005)+1 种基金the Gansu Natural Science Foundation(No.25JRRA467)the Key Research Program of the Chinese Academy of Sciences(No.XDPB15)。
文摘Neutron-rich boron,carbon,and nitrogen isotopes have garnered extensive experimental and theoretical interest.In the present work,we conducted a comprehensive study of these nuclei by utilizing ab initio valence-space in-medium similarity renormalization group calculations with chiral nucleon-nucleon and three-nucleon interactions.First,we systematically calculated the spectra of nuclei.Our results align well with the available experimental data,which are comparable to phenomenological shell model calculations.Subsequently,the evolution of the N=14 and N=16 shell gaps is discussed based on the calculated spectra and the effective single-particle energies.Our calculations suggest that the N=14 neutron subshell is present in the oxygen isotopes but disappears in the boron,carbon,and nitrogen isotopic chains.Moreover,the N=16 subshell is present in all isotopes but gradually decreases from^(24)O to^(21)B.These results provide valuable information for future studies.
基金supported by the National Natural Science Foundation of China(Nos.22207036,22277034,22477034,and 22107033)Interdisciplinary Research Program of Huazhong University of Science and Technology(No.2023JCYJ037)International Cooperation Project of Hubei Provincial Key R&D Plan(No.2023EHA040)。
文摘Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers,dauroxonanols A(1)and B(2),possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.0^(4.17).0^(14.18)]octadecane core skeleton,were isolated from Rhododendron dauricum.The nuclear magnetic resonance(NMR)spectra of 1 and 2 showed very broad resonances,and^(13)C NMR spectrum of 1 exhibited only 13 instead of 22 carbon resonances.These broadening or missing NMR resonances led to a great challenge to elucidate their structures using NMR data analysis.Their structures and absolute configurations of 1 and 2 were finally determined by single crystal X-ray diffraction analysis,chiral separation,and electronic circular dichroism(ECD)calculations.Plausible biosynthetic pathways for 1 and 2 are proposed.Conformational analysis,density functional theory(DFT)calculations,and dynamic NMR assigned the coalescent NMR phenomena of 1 and 2 to the conformational changes of the flexible oxonane ring.Dauroxonanols A(1)and B(2)showed potentα-glucosidase inhibitory activities,2-8 times potent than acarbose,an antidiabetic drug targetingα-glucosidase in clinic.
基金supported and funded internally through Dr. Catherine Johnson's research funds at Missouri S&T
文摘This study investigates the application of Gurney and flight of fragment equations,typically used to predict metal fragment velocities,in modeling the water jet behavior.Three shotgun cartridge sizes were used as the energy source:2.59 g,5.83 g,and 7.13 g.Two configurations were tested:standard(full-barrel water load)and"negative 8"(partial water load).High-speed footage captured water column velocities,and Gurney models,including infinitely tamped and open-faced configurations,combined with the flight of fragment model were used to assess prediction accuracy.Results showed charge strength significantly affects water column velocity,with higher strengths yielding greater stability and velocity retention over distance.The infinitely tamped Gurney model closely predicted experimental velocities,deviating by as little as 1.4%for standard charges and 2.8% for negative 8 charges.Additionally,interesting dynamics such as a 1-2°rise in jet height and the rear overtaking the front was observed.These findings have significant implications for optimizing PAN disruptors and enhancing performance in high-velocity fluid applications and explosive breaching systems.
基金support from the National Natural Science Foundation of China(52174290).
文摘To explain the influence mechanism of MgO on the consolidation and reduction characteristics of roasted iron pellets,the properties and structure of pellets were investigated from multi-dimensions.It indicated that the MgO addition decreased the reduction swelling index(RSI)and reduction degree of pellets in both CO and H_(2)atmospheres.During the stepwise reduction process of Fe2O3→Fe3O4→FeO,the reduction behaviour of pellets in CO and H_(2)was similar,while the reduction rate of pellets in H_(2)atmosphere was almost twice as high as that in CO atmosphere.During the stepwise reduction process of FeO→Fe,the RSI of pellets showed a logarithmic increase in CO atmosphere and a linear decrease in H_(2)atmosphere.As investigated by first-principles calculations,C and Fe mainly formed chemical bonds,and the CO reduction process released energy,promoting the formation of iron whiskers.However,H and Fe produced weak physical adsorption,and the H_(2)reduction process was endothermic,inhibiting the generation of iron whiskers.With Mg2+doping in FexO,the nucleation region of iron whiskers expanded in CO reduction process,and the morphology of iron whiskers transformed from“slender”to“stocky,”reducing RSI of the pellets.
基金supported by the National Key R&D Program of China(Nos.2024YFA1610900 and 2023YFA1606401)the National Natural Science Foundation of China(Nos.12335007 and 12035001)the United Kingdom Science and Technology Facilities Council(No.ST/V001108/1)。
文摘High multipole electromagnetic transitions are rare in nature.The highest-multipole transition observed in atomic nuclei is the electric hexacontatetrapole E6 transition from the T_(1/2)=2.54(2)-min J^(π)=1_(9/2)-isomer to the 7/2^(-)ground state in^(53)Fe with an angular momentum change of six units.In the present work,we performed ab initio calculations for this unique case by employing chiral effective field theory(EFT)forces.The in-medium similarity renormalization group is used to derive the valence-space effective Hamiltonian and multipolar transition operators.Bare nucleon charges were used in all the multipolar transition rate calculations,providing good agreement with the experimental data.The valence space takes the full fp shell.In^(53)Fe,the low-lying states were dominated by the 0f_(7/2)component.Two different versions of the chiral EFT two-plus three-nucleon interaction were used to test the dependence on the interaction used.We also tested the convergence of the transition rate calculations against the harmonic oscillator parameter hΩand basis truncations e_(max)and E_(3max)for twoand three-nucleon forces,respectively.
基金financially supported by the National Natural Science Foundation of China(No.52171141)the Fund of Natural Science Special(Special Post)Research Foundation of Guizhou University(No.2023-032)the Fund of Research Foundation of Guizhou University(No.2024-33)
文摘Currently,the development of high-efficiency two-dimensional(2D)transistors is still hindered by the limited availability of suitable semiconductors and the contact resistance between the metal contact and the 2D semiconductors.Endeavors to address these challenges are highly desired.In this study,we conducted a comprehensive exploration of the potential 2D transition metal dinitrides(TMN_(2)s,TM=all the 3d,4d and 5d transition metals)with hexagonal(h-)and trigonal(t-)phases through systematic first-principles calculations.Among all h-TMN_(2)s and t-TMN_(2)s structures,we identified 8 TMN_(2)s that exhibit dynamical and thermal stability at room temperature.Of these,the h-TiN_(2),h-ZrN_(2)and h-HfN_(2)arefound to be semiconductors,and their direct bang gap,calculated at the HSE06 level,are 1.48,1.96 and 2.64 eV,respectively.The electron and hole mobility(μ_(e)andμ_(h))of these three structures exceed 1×10^(4)and1×10^(3)cm^(2)·V^(-1)·s^(-1),respectively.Especially,theμeof h-TiN_(2)amounts to 2.5×10^(4)cm^(2)·V^(-1)·s^(-1),and theμhof h-ZrN_(2)reaches to 7.7×10^(3)cm^(2)·V^(-1)·s^(-1).Importantly,unlike the MoS_(2)system,h-TMN_(2)forms Ohm contacts with both transition metals(e.g.,Cu)and 2D metals(e.g.,graphene),with tunneling possibilities exceeding 50%in the Cu system.These outstanding intrinsic semiconductor properties and contact characteristics exhibited by h-TMN_(2)highlight the immense potential of transition metal dinitrides in driving the advancement of next-generation information devices.Our findings significantly broaden the range of 2D materials and provide valuable insights for the development of high-eficiency 2D information devices.
基金supported by the National Key R&D Program of China(Grant Nos.2024-YFA1408303 and 2022YFA1403301)the National Natural Sciences Foundation of China(Grant Nos.12474247 and 92165204)+1 种基金support from Guangdong Provincial Key Laboratory of Magnetoelectric Physics and Devices(Grant No.2022B1212010008)Research Center for Magnetoelectric Physicsof Guangdong Province(Grant No.2024B0303390001).
文摘Magnets exhibiting the Kitaev interaction,a bond-dependent magnetic interaction in honeycomb lattices,are generally regarded as promising candidates for hosting novel phenomena like quantum spin liquid states.However,realizing such magnets remains a significant challenge.Recently,some studies have suggested honeycomb magnets A_(3)Ni_(2)XO_(6)(A=Li,Na;X=Bi,Sb)with a high spin S=1 could serve as potential candidates for realizing strong Kitaev interactions.In this work,we systematically investigate their magnetic properties,with a particular emphasis on their Kitaev interactions,using first-principles calculations and Monte Carlo simulations.Our results indicate that all A_(3)Ni_(2)XO_(6)compounds are zigzag antiferromagnets,and their magnetic moments almost tend to be out of plane.We find that their dominant magnetic interactions are the nearest-neighbor ferromagnetic and third-nearest-neighbor antiferromagnetic Heisenberg interactions,while their Kitaev interactions are extremely weak.By analyzing their electronic structures and the mechanism of generating their magnetic interactions,we reveal that either artificially tuning spin-orbit coupling or applying strain cannot produce sufficient spin-orbit entangled states to realize the intriguing Kitaev interactions.Our work advances the understanding of the magnetism in A_(3)Ni_(2)XO_(6)compounds and provides insights for further exploration of Kitaev physics in honeycomb magnets.
文摘In this paper, cold simulation experiments and numerical calculations are conducted to predict 3 D flow field aerodynamics for an oil furnace after being retrofitted due to its fuel variation. K ε model and SIMPLE program under body fit coordination (BFC) system, in which TTM non orthogonal method is used to control the irregular geometric boundary, are adopted to solve the control equations. Model tests are conducted to check the calculation results, showing that they are in agreement with each other. Three different alternatives with different side window locations are also calculated to optimize the designs. The field retrofitting results show that the combination of cold tests with numerical calculations has prosperous application in retrofitting or renewing medium and small boilers.
文摘We investigated the structural evolution and elecfronic properties of ConC3-/0 and ConC4-/0 （n=1-4） clusters by using mass-selected photoelectron spectroscopy and density functional theory calculations. The adiabatic and vertical detachment energies of CO1-4C3- and COl-4C4- were obtained from their photoelectron spectra. By comparing the theoretical results with the experimental data, the global minimum structures were determined. The results indicate that the carbon atoms of ConC3-/0 and ConC4-/0 （n=1-4） are separated from each other gradually with increasing number of cobalt atoms but a C2 unit still remains at n=4. It is interesting that the Co2C3- and Co2C4- anions have planar structures whereas the neutral Co2C3 and Co2C4 have linear structures with the Co atoms at two ends. The Co3C3- anion has a planar structure with a Co2C2 four-membered ring and a Co3C four-membered ring sharing a Co-Co bond, while the neutral Co3C3 is a three-dimensional structure with a C2 unit and a C atom connecting to two faces of the Co3 triangle.
文摘Two-phase equilibria between the ferromagnetic fcc and the paramagnetic fcc phase from 800 ℃ to 900 ℃ in the Co-rich region have been detected by the diffusion couple technique. Two phase separation region of the fcc has been confirmed along the Curie temperature.The phase equilibria including the present results and the thermodynamic data of the Co-Cr system reported in the literature were analyzed on the basis of the thermodynamic evaluation. A set of thermodynamic values for the liquid, fcc, hcp, bcc, sigma phases was obtained. The calculated phase equilibria were in good agreement with most of the experimental data.
基金supported by the National Key Research and Development Program of China(No.2016YFC0600509)the National Natural Science Foundation of China(No.41772069)+1 种基金the China Geological Survey Program(Nos.1212011085490,12120113089600,12120114028701)the Fundamental Research Funds for the Central University(No.2652017259)
文摘GeoPyTool is an open source application developed for geological calculations and plots,such as geochemical classification,parameter calculation,basic statistical analysis and diagrams for structural geology.More than acting as a link from raw data stored in Microsoft Excel■(MS Excel)files to vector graphic files,GeoPyTool includes recently developed routines that have not been included in previous software,such as the calculation of the Ce(Ⅳ)/Ce(Ⅲ)ratio for zircons as a method to examine the temporal evolution of oxygen fugacity in the magmatic source for igneous rocks,and the temperature calculator with titanium in zircon and zirconium in rutile.Besides these routines,GeoPyTool also allows users to load any figure from articles or books as a base map.As a Python-based crossplatform program,GeoPyTool works on Windows?,MacOS X?and GNU/Linux.GeoPyTool can do the whole process from data to results without the dependence of Microsoft Excel?,CorelDraw?and other similar software.It takes Excel?XLSX and CSV(Comma Separated Value)as the formats of both the input data source files and the output calculation results files.The figures generated by GeoPyTool can be saved as portable network graphics(PNG),scalable vector graphics(SVG)or portable document format(PDF).Another highlight of GeoPyTool is the multilingual support,the official versio n of GeoPyTool supports both Chinese and English,and additional languages can be loaded through interface files.GeoPyTool is still in the development stage and will be expanded with further geochemical and structural geology routines.As an open source project,all source code of GeoPyTool are accessible on Github(https://github.com/GeoPyTool/GeoPyTool).Users with Python experience can join in the development team and build more complex functions expanding the capabilities of GeoPyTool.
文摘Three dimensional diagnostic,semidiagnostic and prognostic models in the σ coordinate are used to compute the current in the East China Sea with wind and hydrographic data obtained from the investigation of ocean fluxes in the East China Sea during the cruise of April 1994.The computed results show that:the density and velocity fields and so on have been adjusted when time t ≈ 23 d, i.e.,the solution of semidiagnostic calculation has been obtained.The quasi steady state solution also has been reached after about 60 d.Comparing the results of diagnostic calculation with those of semidiagnostic and prognostic calculations,it is found that they agree qualitatively.For example,they all show that:(1)The Kuroshio flows along the shelf break of 200～1 000 m isobaths;(2)In the southeastern part of the computational region there is a stronger counter current with an anticyclonic eddy;(3)The volume transport through Section PN is about 30×10 6m 3/s and so on.However there are some quantitative differences between them.For example,(1)For the semidiagnostic results the Kuroshio current is stronger and clearer than that for diagnostic results and the Kuroshio width is more narrow than that for diagnostic results.This shows that the semidiagnostic calculation can better reflect the topography effect;(2)In most computed region the vertical component of velocity intensifies for semidiagnostic result,especially on the shelf break.Comparing the results of semidiagnostic calculation with those of prognostic calculation,they agree qualitatively,and also agree quantitatively in the middle of computed region.
基金supported by the National Nature Science Foundation of China (No. 50771046)the Foundation from Department of Education of Guangdong Province (No. C10179)
文摘The physical characters and electrochemical properties of various phases in a Sn-Zn electrode, such as formation energy, plateau potential, specific capacity, as well as volume expansion, were calculated by the first-principles plane-wave pseudo-potential method based on the den- sity functional theory. Sn-Zn films were also deposited on copper foils by an electroless plating technique. The actual composition and chemical characters were explored by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, plasma atomic emission spectrometry （ICP）, and constant current charge/discharge measurements （CC）. The results show that separation phases with tin and zinc including a small quantity of Cu6Sn5 phase were obtained, the initial lithium insertion capacity of the Sn-Zn film was 661 mAh/g, and obvious potential pla- teaus of about 0.4 V and 0.7 V were displayed, which is in accordance with the results of theoretical calculations. The capacity of the Sn-Zn film decreased seriously with the increase of cycle number.
基金the National Natural Science Foundation of China under grant No.10374076.
文摘The electronic structures of CuS2, CuSe2 and CuTe2 with pyrite structures, within the framework the density-functional theory have been investigated. The calculated results explained the recent experimental results which show that there is no clear indication of strong electron correlations in the electronic properties of Cu pyrites, due to the dominant chalcogen p character rather than d characteristic of Cu at the Fermi level.
