Understanding Bonding Nature ofα-Keggin Polyoxometalates[XW_(12)O_(40)]^(n−)(X=Al,Si,P,S):A Generalized Superatomic Perspective

α-Keggin polyoxometalates(POMs)[XW_(12)O_(40)]^(n−)(X=Al,Si,P,S)are widely used in batteries owing to their remarkable redox activity.However,the mechanism underlying the applications appears inconsistent with the widely accepted covalent bonding nature.Here,first-principles calculations show that XW_(12)are core–shell structures composed of a shell and an XO_(4)^(n−)core,both are stabilized by covalent interactions.Interestingly,owing to the presence of a substantial number of electrons in W_(12)O_(36)shell,the frontier molecular orbitals of XW_(12)are not only strongly delocalized but also exhibit superatomic properties with high-angular momentum electrons that do not conform to the Jellium model.Detailed analysis indicates that energetically high lying filled molecular orbitals(MOs)have reached unusually high-angular momentum characterized by quantum number K or higher,allowing for the accommodation of numerous electrons.This attribute confers strong electron acceptor ability and redox activity to XW_(12).Moreover,electrons added to XW_(12)still occupy the K orbitals and will not cause rearrangement of the MOs,thereby maintaining the stability of these structures.Our findings highlight the structure–activity relationship and provide a direction for tailor-made POMs with specific properties at atomic level.

Recension of boron nitride phase diagram based on high-pressure and high-temperature experiments

Cubic boron nitride and hexagonal boron nitride are the two predominant crystalline structures of boron nitride.They can interconvert under varying pressure and temperature conditions.However,this transformation requires overcoming significant potential barriers in dynamics,which poses great difficulty in determining the c-BN/h-BN phase boundary.This study used high-pressure in situ differential thermal measurements to ascertain the temperature of h-BN/c-BN conversion within the commonly used pressure range(3-6 GPa)for the industrial synthesis of c-BN to constrain the P-T phase boundary of h-BN/c-BN in the pressure-temperature range as much as possible.Based on the analysis of the experimental data,it is determined that the relationship between pressure and temperature conforms to the following equation:P=a+1/bT.Here,P denotes the pressure(GPa)and T is the temperature(K).The coefficients are a=-3.8±0.8 GPa and b=229.8±17.1 GPa/K.These findings call into question existing high-pressure and high-temperature phase diagrams of boron nitride,which seem to overstate the phase boundary temperature between c-BN and h-BN.The BN phase diagram obtained from this study can provide critical temperature and pressure condition guidance for the industrial synthesis of c-BN,thus optimizing synthesis efficiency and product performance.

Excitation and ionization of OCS molecules in strong UV and NIR laser fields

Rydberg state excitation(RSE) is a highly non-linear physical phenomenon that is induced by the ionization of atoms or molecules in strong femtosecond laser fields. Here we observe that both parent and fragments(S, C, OC) of the triatomic molecule carbonyl sulfide(OCS) can survive strong 800 nm or 400 nm laser fields in high Rydberg states. The dependence of parent and fragment RSE yields on laser intensity and ellipticity is investigated in both laser fields, and the results are compared with those for strong-field ionization. Distinctly different tendencies for laser intensity and ellipticity are observed for fragment RSE compared with the corresponding ions. The mechanisms of RSE and strong-field ionization of OCS molecules in different laser fields are discussed based on the experimental results. Our study sheds some light on the strong-field excitation and ionization of molecules irradiated by femtosecond NIR and UV laser fields.

Core level excitation spectra of La and Mn ions in LaMnO3

Manganese-based perovskite is popular for research on ferromagnetic materials,and its spectroscopic studies are essential for understanding its electronic structure,dielectric,electrical,and magnetic properties.In this paper,the M-edge spectra of La ions and the M-edge,L-edge,and K-edge spectra of Mn ions in LaMnO3 are calculated by considering both the free-ion multiplet calculation and the crystal field effects.We analyze spectral shapes,identify peak origins,and estimate the oxidation states of La and Mn ions in LaMnO3 theoretically.It is concluded that La ions in LaMnO3 predominantly exist in the trivalent state,while Mn ions exist primarily in the trivalent state with a minor presence of tetravalent ions.Furthermore,the calculated spectra are in better conformity with the experimental spectra when the proportion of Mn3+is 90%and Mn4+is 10%.This article enhances our comprehension of the oxidation states of La and Mn within the crystal and also provides a valuable guidance for spectroscopic investigations of other manganates.

Design of a 3D-printed liquid lithium divertor target plate and its interaction with high-density plasma

A liquid Li divertor is a promising alternative for future fusion devices.In this work a new divertor model is proposed,which is processed by 3D-printing technology to accurately control the size of the internal capillary structure.At a steady-state heat load of 10 MW m^(-2),the thermal stress of the tungsten target is within the bearing range of tungsten by finite-element simulation.In order to evaluate the wicking ability of the capillary structure,the wicking process at 600℃ was simulated by FLUENT.The result was identical to that of the corresponding experiments.Within 1 s,liquid lithium was wicked to the target surface by the capillary structure of the target and quickly spread on the target surface.During the wicking process,the average wicking mass rate of lithium should reach 0.062 g s^(-1),which could even supplement the evaporation requirement of liquid lithium under an environment>950℃.Irradiation experiments under different plasma discharge currents were carried out in a linear plasma device(SCU-PSI),and the evolution of the vapor cloud during plasma irradiation was analyzed.It was found that the target temperature tends to plateau despite the gradually increased input current,indicating that the vapor shielding effect is gradually enhanced.The irradiation experiment also confirmed that the 3D-printed tungsten structure has better heat consumption performance than a tungsten mesh structure or multichannel structure.These results reveal the application potential and feasibility of a 3D-printed porous capillary structure in plasma-facing components and provide a reference for further liquid-solid combined target designs.

Low-energy inelastic electron scattering from carbon monoxide:Excitation and de-excitation of the X^(1)Σ^(+),a^(3)Π,a'^(3)∑^(+),A^(1)Π,d^(3)Δ,e^(3)∑^(-),I^(1)∑^(-)and D^(1)Δelectronic states

Cross-sections for electronic excitation and de-excitation among the ground state and lowest-lying seven electronic excited states of carbon monoxide(CO)by low-energy electron impact are computed using the R-matrix method.The excitation cross-sections from the ground state to the electronic states a^(3)Π,a'^(3)Σ^(+)+and A^(1)Πagree with previous experimental and theoretical results.In addition,the cross-sections for the I^(1)Σ^(+)-and D^(1)Δstates of CO,which will cascade to CO a'^(3)Σ^(+)+and A^(1)Πstates,are calculated.Furthermore,in contrast to the typical increase in electronic excitation cross-sections with collision energy,the de-excitation cross-sections show a negative trend with increasing energy.

Stability and melting behavior of boron phosphide under high pressure

Boron phosphide(BP)has gained significant research attention due to its unique photoelectric and mechanical properties.In this work,we investigated the stability of BP under high pressure using x-ray diffraction and scanning electron microscope.The phase diagram of BP was explored in both B-rich and P-rich environments,revealing crucial insight into its behavior at 5.0 GPa.Additionally,we measured the melting curve of BP from 8.0 GPa to 15.0 GPa.Our findings indicate that the stability of BP under high pressure is improved within B-rich and P-rich environments.Furthermore,we report a remarkable observation of melting curve frustration at 10.0 GPa.This study will enhance our understanding of stability of BP under high pressure,shedding light on its potential application in semiconductor,thermal,and light-transmitting devices.

Theoretical investigation of excited dipole bound states of alkali-containing diatomic anions

Information about electronic excited states of molecular anions plays an important role in investigating electron attachment and detachment processes.Here we present a high-level theoretical study of the electronic structures of 12 alkali-metal-containing diatomic anions MX-(MX = LiH,LiF,LiCl,NaF,NaCl,NaBr,RbCl,KCl,KBr,RbI,KI and CsI).The equation-of-motion electron-attachment coupled-cluster singles and doubles(EOM-EA-CCSD) method is used to calculate the electron binding energies(EBEs) of 10 electronic excited states of each of the 12 molecule anions.With addition of different s-/p-/d-type diffusion functions in the basis set,we have identified possible excited dipole bound states(DBSs) of each anion.With the investigation of EBEs on the 12 MXs with dipole moment(DM) up to 12.1 D,we evaluate the dependence of the number of anionic excited DBSs on molecular DM.The results indicate that there are at least two or three DBSs of anions with a molecular DM larger than 7 D and a molecule with DM > 10 D can sustain a π-DBS of the anion.Our study has some implications for the excited DBS electronic states of alkali-metal-containing diatomic molecules.

High-order harmonic generation of ZnO crystals in chirped and static electric fields

High harmonic generation in ZnO crystals under chirped single-color field and static electric field are investigated by solving the semiconductor Bloch equation(SBE). It is found that when the chirp pulse is introduced, the interference structure becomes obvious while the harmonic cutoff is not extended. Furthermore, the harmonic efficiency is improved when the static electric field is included. These phenomena are demonstrated by the classical recollision model in real space affected by the waveform of laser field and inversion symmetry. Specifically, the electron motion in k-space shows that the change of waveform and the destruction of the symmetry of the laser field lead to the incomplete X-structure of the crystal-momentum-resolved(k-resolved) inter-band harmonic spectrum. Furthermore, a pre-acceleration process in the solid four-step model is confirmed.

Photoelectron momentum distributions of triatomic CO_(2)molecules by circularly polarized attosecond pulses

Molecular-frame photoelectron momentum distributions(MF-PMDs)have been studied for imaging molecular structures.We investigate the MF-PMDs of CO_(2)molecules exposed to circularly polarized(CP)attosecond laser pulses bysolving the time-dependent Schrodinger equations based on the single-active-electron approximation frames.Results showthat high-frequency photons lead to photoelectron diffraction patterns,indicating molecular orbitals.These diffractionpatterns can be illustrated by the ultrafast photoionization models.However,for the driving pulses with 30 nm,a deviationbetween MF-PMDs and theoretically predicted results of the ultrafast photoionization models is produced because theCoulomb effect strongly influences the molecular photoionization.Meanwhile,the MF-PMDs rotate in the same directionas the helicity of driving laser pulses.Our results also demonstrate that the MF-PMDs in a CP laser pulse are the superpositionof those in the parallel and perpendicular linearly polarized cases.The simulations efficiently visualize molecularorbital geometries and structures by ultrafast photoelectron imaging.Furthermore,we determine the contribution of HOMOand HOMO-1 orbitals to ionization by varying the relative phase and the ratio of these two orbitals.

Pressure-Driven Energy Band Gap Narrowing of λ-N_(2)

Probing the energy band gap of solid nitrogen at high pressures is of importance for understanding pressuredriven changes in electronic structures and insulator-to-metal transitions under high pressure.The λ-N_(2) formed by cold compression is known to be the most stable one in all solid nitrogen phases observed so far.By optimizing the optical system,we successfully measured the high-pressure absorption spectra of λ-N_(2) covering the polymericnitrogen synthetic pressures(124 GPa-165 GPa).The measured optical band gap decreases with increasing pressure,from 2.23 eV at 124 GPa to 1.55 eV at 165 GPa,with a negative pressure coefficient of-18.4 meV/GPa,which is consistent with the result from our ab initio total-energy calculations(-22.6 meV/GPa).The extrapolative metallization pressure for theλ-N_(2) is around 288(18)GPa,which is close to the metallization pressure(280 GPa)for the η-N_(2) expected by previous absorption edge and direct electrical measurements.Our results provide a direct spectroscopic evidence for the pressure-driven band gap narrowing of solid nitrogen.

Splitting of Degenerate Superatomic Molecular Orbitals Determined by Point Group Symmetry

We first confirm an idea obtained from first-principles calculations,which is in line with symmetry theory:Although superatomic molecular orbitals(SAMOs) can be classified according to their angular momentum similar to atomic orbitals,SAMOs with the same angular momentum split due to the point group symmetry of superatoms.Based on this idea,we develop a method to quantitatively modulate the splitting spacing of molecular orbitals in a superatom by changing its structural symmetry or by altering geometric parameters with the same symmetry through expansion and compression processes.Moreover,the modulation of the position crossover is achieved between the lowest unoccupied molecular orbital and the highest occupied molecular orbital originating from the splitting of different angular momenta,leading to an effective reduction in system energy.This phenomenon is in line with the implication of the Jahn–Teller effect.This work provides insights into understanding and regulating the electronic structures of superatoms.

Swelling of K＋, Na＋ and Ca2＋-montmorillonites and hydration of interlayer cations： a molecular dynamics simulation

This paper performs molecular dynamics simulations to investigate the role of the monovalent cations K, Na and the divalent cation Ca on the stability and swelling of montmorillonite. The recently developed CLAYFF force field is used to predict the basal spacing as a function of the water content in the interlayer. The simulations reproduced the swelling pattern of these montmorillonites, suggesting a mechanism of their hydration different （K＋ 〈 Na＋ 〈 Ca2＋） from that of K＋-, Na＋-, and Ca2＋-montmorillonites. In particular, these results indicate that the valence of the cations has the larger impact on the behaviour of clay water systems. It also finds that the differences in size and hydration energy of K＋, Na＋ and Ca2＋ ions have strong implications for the structure of interlayer. This leads to the differences in the layer spacings of the simulated K＋-, Na＋-, and Ca2＋-montmorillonites. Furthermore, these simulations show that the K cations interact strongly with the clay sheets for the dehydrated clay sheets, but for the hydrated clays the Ca cations interact clearly strongly with the clay sheets.

Hexapole State-Selection and Beam Focus of Linear Triatomic Molecules

The state selection and beam focus of linear triatomic molecules （OCS, HCN, ClCN, BrCN and ICN） with doubling states in a hexapole electric field have been numerically realized. The method is based on a quantum mechanical treatment of the molecular Stark energy and a classical mechanical treatment for the molecular trajectory in the field. In linear molecules with doubling states, the second-order Stark effect can be neglected and the doubling states have the same value of J and M. The influences of the molecular properties, state energies, and the apparatus parameters such as molecular beam temperature and length of the hexapole, on the role of state selection and focus have been discussed. The method established here can be taken as a guide for hexapole experiment of orientation of polar molecules.

High-pressure and high-temperature sintering of pure cubic silicon carbide:A study on stress-strain and densification

Silicon carbide(SiC)is a high-performance structural ceramic material with excellent comprehensive properties,and is unmatched by metals and other structural materials.In this paper,raw SiC powder with an average grain size of 5μm was sintered by an isothermal-compression process at 5.0 GPa and 1500?C;the maximum hardness of the sintered samples was31.3 GPa.Subsequently,scanning electron microscopy was used to observe the microscopic morphology of the recovered SiC samples treated in a temperature and extended pressure range of 0-1500?C and 0-16.0 GPa,respectively.Defects and plastic deformation in the SiC grains were further analyzed by transmission electron microscopy.Further,high-pressure in situ synchrotron radiation x-ray diffraction was used to study the intergranular stress distribution and yield strength under non-hydrostatic compression.This study provides a new viewpoint for the sintering of pure phase micron-sized SiC particles.

Modulation of High-Order Harmonic Generation from a Monolayer ZnO by Co-rotating Two-Color Circularly Polarized Laser Fields

By numerically solving the two-dimensional semiconductor Bloch equation,we study the high-order harmonic emission of a monolayer ZnO under the driving of co-rotating two-color circularly polarized laser pulses.By changing the relative phase between the fundamental frequency field and the second one,it is found that the harmonic intensity in the platform region can be significantly modulated.In the higher order,the harmonic intensity can be increased by about one order of magnitude.Through time-frequency analysis,it is demonstrated that the emission trajectory of monolayer ZnO can be controlled by the relative phase,and the harmonic enhancement is caused by the second quantum trajectory with the higher emission probability.In addition,near-circularly polarized harmonics can be generated in the co-rotating two-color circularly polarized fields.With the change of the relative phase,the harmonics in the platform region can be altered from left-handed near-circularly polarization to right-handed one.Our results can obtain high-intensity harmonic radiation with an adjustable ellipticity,which provides an opportunity for syntheses of circularly polarized attosecond pulses.

Generation of quasi-chirp-free isolated attosecond pulses from atoms under the action of orthogonal two-color combined pulse of fundamental frequency and higher intensity second harmonic fields

The intrinsic chirp of high-order harmonic generation is an important factor limiting the production of ultrashort attosecond pulses.Based on numerically solving the time-dependent Schrodinger equation,the generation process of highorder harmonic from the He atom under the action of orthogonal two-color combined pulse of fundamental frequency and higher intensity second harmonic fields is studied.In this paper,we propose to achieve quasi-chirp-free isolated attosecond pulses by superimposing a higher second-harmonic field on the orthogonal direction of the fundamental frequency field.It is found that the high-energy part of its harmonic emission exhibits small chirp characteristics,which can be used to synthesize isolated attosecond pulses.Through the analysis of the wave packets evolution and the classical motion trajectories of the electron,it is demonstrated that the quasi-chirp-free harmonic can be attributed to the simultaneous return of electrons ionized at different times to the parent particle.The influence of the relative phase of the two pulses on the harmonics is further analyzed,and it is observed that this phenomenon is sensitive to the relative phase,but it can still generate isolated attosecond pulses within a certain phase.

Gas-and plasma-driven hydrogen permeation behavior of stagnant eutectic-solid GaInSn/Fe double-layer structure

Gas-driven permeation(GDP)and plasma-driven permeation(PDP)of hydrogen gas through Ga In Sn/Fe are systematically investigated in this work.The permeation parameters of hydrogen through Ga In Sn/Fe,including diffusivity,Sieverts'constant,permeability,and surface recombination coefficient are obtained.The permeation flux of hydrogen through Ga In Sn/Fe shows great dependence on external conditions such as temperature,hydrogen pressure,and thickness of liquid Ga In Sn.Furthermore,the hydrogen permeation behavior through Ga In Sn/Fe is well consistent with the multilayer permeation theory.In PDP and GDP experiments,hydrogen through Ga In Sn/Fe satisfies the diffusion-limited regime.In addition,the permeation flux of PDP is greater than that of GDP.The increase of hydrogen plasma density hardly causes the hydrogen PDP flux to change within the test scope of this work,which is due to the dissolution saturation.These findings provide guidance for a comprehensive and systematic understanding of hydrogen isotope recycling,permeation,and retention in plasma-facing components under actual conditions.

Atomic structure and transition properties of H-like Al in hot and dense plasmas

The atomic structure and transition properties of H-like Al embedded in hot and dense plasmas are investigated using modified GRASP2 K code. The plasma screening effect on the nucleus is described using the self-consistent field ion sphere model. The effective nuclear potential decreases much more quickly with increasing average free electron density,but increases slightly with increasing electron temperature. The variations of the transition energies, transition probabilities,and oscillator strengths with the free electron density and electron temperature are the same as that of the effective nuclear potential. The results reported in this work agree well with other available theoretical results and are useful for plasma diagnostics.

Study of Imidazolium Ionic Liquids:Temperature-dependent Fluorescence and Molecular Dynamics Simulation

The steady-state fluorescence spectra and molecular dynamics simulations were explored to investigate the temperature dependent organization in some imidazolium ionic liquids：1-butyl-3-methylimidazolium hexafluo-rophosphate（[bmim][PF6]）,1-ethyl-3-methylimidazolium ethylsulfate（[emim][EtSO4]） and 1-butyl-3-methylimida-zolium tetrafluoroborate（[bmim][BF4]）.The pure room temperature ionic liquids（ILs） exhibit a large red shift at more than an excitation wavelength of around 340 nm,which demonstrates the heterogeneous nature of the liquids.Furthermore,the fluorescence spectra of the ionic liquids were found to be temperature-dependent.The emission intensity gradually decreased with increasing temperature for the neat ionic liquids and the mixed solutions of [bmim][BF4]-H2O,which was the special phenomena induced by not only the local structure but also the viscosity.The molecular dynamics simulation further confirms that the structures of ionic liquids are sensitive to the surroun-ding environment because of the aggregation degree of ILs.