Application of the HSAB principle for the quantitative analysis of nucleophilicity/basicity of organic compounds with lone-pair electrons

Based on the density functional theory,we described here a method to investigate the quantitative relationship between nucleophilicity/basicity and HSAB-theory-based properties of compounds with lone-pair electrons.Descriptors including global softness,Fukui function,local softness and local mulliken charge were calculated at SVWN/DN~* level of DFT with PC Spartan Pro.Nucleophilicity and basicity of 28 selected compounds were classified based on intensity.BP algorithm of artificial neural network(ANN) was employed to study the relationship between the descriptors and nucleophilicity/basicity.Cross-validation was carried out to avoid the over-fitting in training of ANN.A BP network was trained to quantify the relationship between HSAB-theory-based properties and nucleophilicity/basicity of compounds with lone-pair electrons.The results show that the prediction based on the network matches with the experimental results well.The local softness and Fukui function have a better relationship with nucleophilicity and local mulliken charge than with the basicity.The trained BP network could be utilized for predicting the nucleophilicity/basicity of compounds or functional groups with lone-pair electrons.

Application of the HSAB principle for the quantitative analysis of nucleophilicity/basicity of organic compounds with lone-pair electrons

Based on the density functional theory, we described here a method to investigate the quantitative relationship between nucleophilicity/basicity and HSAB-theory-based properties of compounds with lone-pair electrons. Descriptors including global softness, Fukui function, local softness and local mulliken charge were calculated at SVWN/DN＊ level of DFT with PC Spartan Pro. Nucleophilicity and basicity of 28 selected compounds were classified based on intensity. BP algorithm of artificial neural network （ANN） was employed to study the relationship between the descriptors and nucleophilicity/basicity. Cross-validation was carried out to avoid the over-fitting in training of ANN. A BP network was trained to quantify the relationship between HSAB-theory-based properties and nucleophilicity/basicity of compounds with lone-pair electrons. The results show that the prediction based on the network matches with the experimental results well. The local softness and Fukui function have a better relationship with nucleophilicity and local mulliken charge than with the basicity. The trained BP network could be utilized for predicting the nucleophilicity/basicity of compounds or functional groups with lone-pair electrons.

Electrically-driven ultrafast out-of-equilibrium light emission from hot electrons in suspended graphene/hBN heterostructures

Nanoscale light sources with high speed of electrical modulation and low energy consumption are key components for nanophotonics and optoelectronics.The record-high carrier mobility and ultrafast carrier dynamics of graphene make it promising as an atomically thin light emitter which can be further integrated into arbitrary platforms by van der Waals forces.However,due to the zero bandgap,graphene is difficult to emit light through the interband recombination of carriers like conventional semiconductors.Here,we demonstrate ultrafast thermal light emitters based on suspended graphene/hexagonal boron nitride(Gr/hBN)heterostructures.Electrons in biased graphene are significantly heated up to 2800 K at modest electric fields,emitting bright photons from the near-infrared to the visible spectral range.By eliminating the heat dissipation channel of the substrate,the radiation efficiency of the suspended Gr/hBN device is about two orders of magnitude greater than that of graphene devices supported on SiO2or hBN.Wefurther demonstrate that hot electrons and low-energy acoustic phonons in graphene are weakly coupled to each other and are not in full thermal equilibrium.Direct cooling ofhigh-temperature hot electrons to low-temperature acoustic phonons is enabled by the significant near-field heat transfer at the highly localized Gr/hBN interface,resulting in ultrafast thermal emission with up to 1 GHz bandwidth under electrical excitation.It is found thatsuspending the Gr/hBN heterostructures on the SiO2trenches significantly modifies the light emission due to the formation of the optical cavity and showed a~440%enhancement inintensity at the peak wavelength of 940 nm compared to the black-body thermal radiation.The demonstration of electrically driven ultrafast light emission from suspended Gr/hBNheterostructures sheds the light on applications of graphene heterostructures in photonicintegrated circuits,such as broadband light sources and ultrafast thermo-optic phase modulators.

Steering the energy sharing of electrons in nonsequential double ionization with orthogonally polarized two-color field

Using the semiclassical ensemble model,the dependence of relative amplitude for the recollision dynamics in nonsequential double ionization(NSDI)of neon atom driven by the orthogonally polarized two-color field(OTC)laser field is theoretically studied.And the dynamics in two typical collision pathways,recollision-impact-ionization(RII)and recollisionexcitation with subsequent ionization(RESI),is systematically explored.Our results reveal that the V-shaped structure in the correlated momentum distribution is mainly caused by the RII mechanism when the relative amplitude of the OTC laser field is zero,and the first ionized electrons will quickly skim through the nucleus and share few energy with the second electron.As the relative amplitude increases,the V-shaped structure gradually disappears and electrons are concentrated on the diagonal in the electron correlation spectrum,indicating that the energy sharing after electrons collision is symmetric for OTC laser fields with large relative amplitudes.Our studies show that changing the relative amplitude of the OTC laser field can efficiently control the electron–electron collisions and energy exchange efficiency in the NSDI process.

Mott Gap Filling by Doping Electrons through Depositing One Sub-Monolayer Thin Film of Rb on Ca_(2)CuO_(2)Cl_(2)

Understanding the doping evolution from a Mott insulator to a superconductor probably holds the key to resolve the mystery of unconventional superconductivity in copper oxides. To elucidate the evolution of the electronic state starting from the Mott insulator, we dose the surface of the parent phase Ca_(2)CuO_(2)Cl_(2) by depositing Rb atoms, which are supposed to donate electrons to the CuO_(2) planes underneath. We successfully achieved the Rb sub-monolayer thin films in forming the square lattice. The scanning tunneling microscopy or spectroscopy measurements on the surface show that the Fermi energy is pinned within the Mott gap but close to the edge of the charge transfer band. In addition, an in-gap state appears at the bottom of the upper Hubbard band(UHB), and the Mott gap will be significantly diminished. Combined with the Cl defect and the Rb adatom/cluster results, the electron doping is likely to increase the spectra weight of the UHB for the double occupancy. Our results provide information to understand the electron doping to the parent compound of cuprates.

Erratum to“Tunneling Electrons Triggered Energy Transfer between Coherently Coupled Donor-Acceptor Molecules”

In the original publication of my article,“Tunneling Electrons Triggered Energy Transfer between Coherently Coupled Donor-Acceptor Molecules”,which was published in Chinese Journal of Chemical Physics,Vol.37,No.4,pages 497-504,I have identified an innegligible error that requires correction.I apologize for any inconvenience and appreciate the opportunity to clarify it in the following:Error Description:In page 499,since the words “FIG.2(b,d)”in line 78 are mentioned earlier than the words“FIG.1(a)”in line 82 in the submitted manuscript,the order of Figure 1 and Figure 2 are changed automatically in the official publication of the article,which makes the logical relationship of the article confused to a significant degree.

The influence of boundary conditions on the distribution of energetic electrons during collisionless magnetic reconnection

We conducted 2-D particle-in-cell simulations to investigate the impact of boundary conditions on the evolution of magnetic reconnection. The results demonstrate that the boundary conditions are crucial to this evolution. Specifically, in the cases of traditional periodic boundary(PB) and fully-opened boundary(OB) conditions, the evolutions are quite similar before the system achieves the fastest reconnection rate. However, differences emerge between the two cases afterward. In the PB case, the reconnection electric field experiences a rapid decline and even becomes negative, indicating a reversal of the reconnection process. In contrast, the system maintains a fast reconnection stage in the OB case. Suprathermal electrons are generated near the separatrix and in the exhaust region of both simulation cases. In the electron density depletion layer and the dipolarization front region, a larger proportion of suprathermal electrons are produced in the OB case. Medium-energy electrons are mainly located in the vicinity of the X-line and downstream of the reconnection site in both cases. However, in the OB case, they can also be generated in the electron holes along the separatrix. Before the reverse reconnection stage, no high-energy electrons are present in the PB case. In contrast, about 20% of the electrons in the thin and elongated electron current layer are high-energy in the OB case.

The anisotropy of suprathermal electrons in the Martian ionosphere

Suprathermal electrons are an important population of the Martian ionosphere, either produced by photoionization of atmospheric neutrals or supplied from the Solar Wind (SW). This study is dedicated to an in-depth investigation of the pitch angle distribution of suprathermal electrons at two representative energies, 19−55 eV and 124−356 eV, using the extensive measurements made by the Solar Wind Electron Analyzer on board the Mars Atmosphere and Volatile Evolution. Throughout the study, we focus on the overall degree of anisotropy, defined as the standard deviation of suprathermal electron intensity among different directions which is normalized by the mean omni-directional intensity. The available data reveal the following characteristics: (1) In general, low energy electrons are more isotropic than high energy electrons, and dayside electrons are more isotropic than nightside electrons;(2) On the dayside, the anisotropy increases with increasing altitude at low energies but remains roughly constant at high energies, whereas on the nightside, the anisotropy decreases with increasing altitude at all energies;(3) Electrons tend to be more isotropic in strongly magnetized regions than in weakly magnetized regions, especially on the nightside. These observations indicate that the anisotropy is a useful diagnostic of suprathermal electron transport, for which the conversion between the parallel and perpendicular momenta as required by the conservation of the first adiabatic invariant, along with the atmospheric absorption at low altitudes, are two crucial factors modulating the observed variation of the anisotropy. Our analysis also highlights the different roles on the observed anisotropy exerted by suprathermal electrons of different origins.

Re-delocalization of localized d-electrons in VO_(2)(R)-VS_(4)hetero-structure enables high performance of rechargeable Mg-ion batteries

Rechargeable Mg-ion batteries(MIBs)have attracted much more attentions by virtue of the high capacity from the two electrons chemistry.However,the reversible Mg^(2+)diffusion in cathode materials is restricted by the strong interactions between the high-polarized bivalent Mg^(2+)ions and anionic lattice.Herein,we design and propose a hetero-structural VO_(2)(R)-VS_(4)cathode,in which the re-delocalized d-electrons can effectively shield the polarity of Mg^(2+)ions.Theoretically,the electrons should spontaneously transfer from VS_(4)to VO_(2)(R)through the interfaces of hetero-structure due to the lower work function value of VS_(4).Furthermore,the internal electrons transfer lead to the electronic injection into VO_(2)(R)from VS_(4)and the partially broken V-V dimers,indicating the presence of lone pair electrons and charge re-delocalization.Benefiting from the shield effect of re-delocalized electrons,and the weakened attraction between cations and O/S anions enables more S^(2-)-S_(2)^(2-)redox groups to participate the electrochemical reactions and compensate the double charge of Mg^(2+)ions.Accordingly,VO_(2)(R)-VS_(4)hetero-structure exhibits a high specific capacity of 554 mA h g^(-1)at 50 mA g^(-1).It is believed that the charge re-delocalization of cathode extremely boost the Mg^(2+)ions migration for the high-capacity of MIBs.

A statistical analysis of the Kappa-type energy spectrum distribution of radiation belt electrons observed by Van Allen Probes

The energy spectrum of energetic electrons is a key factor representing the dynamic variations of Earth’s Van Allen radiation belts.Increased measurements have indicated that the commonly used Maxwellian and Kappa distributions are inadequate for capturing the realistic spectral distributions of radiation belt electrons.Here we adopt the Kappa-type(KT)distribution as the fitting function and perform a statistical analysis to investigate the radiation belt electron flux spectra observed by the Van Allen Probes.By calculating the optimal values of the key KT distribution parameters(i.e.,κandθ2)from the observed spectral shapes,we fit the radiation belt electron fluxes at different L-shells under different geomagnetic conditions.In this manner,we obtain typical values of the KT distribution parameters,which are statistically feasible for modeling the radiation belt electron flux profiles during either geomagnetically quiet or active periods.A comparison of the KT distribution model results with those using the Maxwellian or Kappa distribution reveals the advantage of the KT distribution for studying the overall properties of the radiation belt electron spectral distribution,which has important implications for deepening the current understanding of the radiation belt electron dynamics under evolving geomagnetic conditions.

Nonlinear ion acoustic waves in multicomponent plasmas with nonthermal electrons-positron and bipolar ions

This paper studied the propagating characteristics of(2+1)-dimensional nonlinear ion acoustic waves in a multicomponent plasma with nonthermal electrons,positrons,and bipolar ions.The dispersion relations are initially explored by using the small amplitude wave's dispersion relation.Then,the Sagdeev potential method is employed to study large amplitude ion acoustic waves.The analysis involves examining the system's phase diagram,Sagdeev potential function,and solitary wave solutions through numerical solution of an analytical process in order to investigate the propagation properties of nonlinear ion acoustic waves under various parameters.It is found that the propagation of nonlinear ion acoustic waves is subject to the influence of various physical parameters,including the ratio of number densities between the unperturbed positrons,electrons to positive ions,nonthermal parameters,the mass ratio of positive ions to negative ions,and the charge number ratio of negative ions to positive ions,the ratio of the electrons'temperature to positrons'temperature.In addition,the multicomponent plasma system has a compressive solitary waves with amplitude greater than zero or a rarefactive solitary waves with amplitude less than zero,in the meantime,compressive and rarefactive ion acoustic wave characteristics depend on the charge number ratio of negative ions to positive ions.

The Lone Pair Electrons in Post-Transition Metal and Their Contribution to Optical Response

The stereochemically active lone pairs around post-transition metal atoms play an important role in determining distorted lattice structure and optical response.The lone pair electrons are characterized by crystal orbitals,electron localization function(ELF)and partial density of states(PDOS).Birefringence is evaluated by means of a Born effective charge approach based on modern polarization theory.The origin of the different responses of birefringence and second-harmonic generation(SHG)is explored,as well as the effect of spin-orbit coupling(SOC)on the band structure and optical properties is explored.The study of this paper can help to deeply understand the lone pairs and their contribution to optical property.

Bioelectronic medicine in modulation of cortical spreading depolarization and beyond

Bioelectronic interventions,specifically trigeminal nerve st imulat ion(TNS),have attracted considerable attention in conditions where cortical spreading depolarizations(CSDs)accompanied by compromised cerebral perfusion may exacerbate neurological damage.While pharmacological interventions have demonstrated initial potential in addressing CSDs,a standardized treatment approach has not yet been established.The objective of this perspective is to explore emerging bioelectronic methodologies for addressing CSDs,particularly emphasizing TNS,and to underscore TNS’s capacity to enhance neurovascular coupling and cerebral perfusion.

Optimizing electronic structure through point defect engineering for enhanced electrocatalytic energy conversion

Point defect engineering endows catalysts with novel physical and chemical properties,elevating their electrocatalytic efficiency.The introduction of defects emerges as a promising strategy,effectively modifying the electronic structure of active sites.This optimization influences the adsorption energy of intermediates,thereby mitigating reaction energy barriers,altering paths,enhancing selectivity,and ultimately improving the catalytic efficiency of electrocatalysts.To elucidate the impact of defects on the electrocatalytic process,we comprehensively outline the roles of various point defects,their synthetic methodologies,and characterization techniques.Importantly,we consolidate insights into the relationship between point defects and catalytic activity for hydrogen/oxygen evolution and CO_(2)/O_(2)/N_(2) reduction reactions by integrating mechanisms from diverse reactions.This underscores the pivotal role of point defects in enhancing catalytic performance.At last,the principal challenges and prospects associated with point defects in current electrocatalysts are proposed,emphasizing their role in advancing the efficiency of electrochemical energy storage and conversion materials.

Constructing Donor–Acceptor‑Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li^(+)Migration in Quasi‑Solid‑State Battery

Regulation the electronic density of solid-state electrolyte by donor–acceptor(D–A)system can achieve highly-selective Li^(+)transportation and conduction in solid-state Li metal batteries.This study reports a high-performance solid-state electrolyte thorough D–A-linked covalent organic frameworks(COFs)based on intramolecular charge transfer interactions.Unlike other reported COFbased solid-state electrolyte,the developed concept with D–A-linked COFs not only achieves electronic modulation to promote highly-selective Li^(+)migration and inhibit Li dendrite,but also offers a crucial opportunity to understand the role of electronic density in solid-state Li metal batteries.The introduced strong electronegativity F-based ligand in COF electrolyte results in highlyselective Li^(+)(transference number 0.83),high ionic conductivity(6.7×10^(-4)S cm^(−1)),excellent cyclic ability(1000 h)in Li metal symmetric cell and high-capacity retention in Li/LiFePO_(4)cell(90.8%for 300 cycles at 5C)than substituted C-and N-based ligands.This is ascribed to outstanding D–A interaction between donor porphyrin and acceptor F atoms,which effectively expedites electron transferring from porphyrin to F-based ligand and enhances Li^(+)kinetics.Consequently,we anticipate that this work creates insight into the strategy for accelerating Li^(+)conduction in high-performance solid-state Li metal batteries through D–A system.

Bound-state electrons synergy over photochromic high-crystalline C_(3)N_(5) nanosheets in enhancing charge separation for photocatalytic H_(2) production

Solar-driven water splitting for photocatalytic hydrogen evolution is considered a highly promising and costeffective solution to achieve a stable renewable energy supply.However,the sluggish kinetics of electron-hole pairs’separation poses challenges in attaining satisfactory hydrogen production efficiency.Herein,we synthesized the exceptional performance of highly crystalline C_(3)N_(5)(HC–C_(3)N_(5))nanosheet as a photocatalyst,demonstrating a remarkable hydrogen evolution rate of 3.01 mmol h^(-1)g^(-1),which surpasses that of bulk C_(3)N_(5)(B–C_(3)N_(5))by a factor of 3.27.Experimental and theoretical analyses reveal that HC-C_(3)N_(5)nanosheets exhibit intriguing macroscopic photoinduced color changes,effectively broadening the absorption spectrum and significantly enhancing the generation of excitons.Besides,the cyano groups in HC-C_(3)N_(5)efficiently captures and converts photoexcited electrons into bound states,thereby prolonging their lifetimes and effectively separating electrons and holes into catalytically active regions.This research provides valuable insights into the establishment of bound electronic states for developing efficient photocatalysts.

Non-uniform electron density estimation based on electromagnetic wave attenuation in plasma

The surface of a high-speed vehicle reentering the atmosphere is surrounded by plasma sheath.Due to the influence of the inhomogeneous flow field around the vehicle,understanding the electromagnetic properties of the plasma sheath can be challenging.Obtaining the electron density of the plasma sheath is crucial for understanding and achieving plasma stealth of vehicles.In this work,the relationship between electromagnetic wave attenuation and electron density is deduced theoretically.The attenuation distribution along the propagation path is found to be proportional to the integral of the plasma electron density.This result is used to predict the electron density profile.Furthermore,the average electron density is obtained using a back-propagation neural network algorithm.Finally,the spatial distribution of the electron density can be determined from the average electron density and the normalized derivative of attenuation with respect to the propagation depth.Compared to traditional probe measurement methods,the proposed approach not only improves efficiency but also preserves the integrity of the plasma environment.

Electronic band structures of topological kagome materials

The kagome lattice has garnered significant attention due to its ability to host quantum spin Fermi liquid states.Recently,the combination of unique lattice geometry,electron–electron correlations,and adjustable magnetism in solid kagome materials has led to the discovery of numerous fascinating quantum properties.These include unconventional superconductivity,charge and spin density waves(CDW/SDW),pair density waves(PDW),and Chern insulator phases.These emergent states are closely associated with the distinctive characteristics of the kagome lattice's electronic structure,such as van Hove singularities,Dirac fermions,and flat bands,which can exhibit exotic quasi-particle excitations under different symmetries and magnetic conditions.Recently,various quantum kagome materials have been developed,typically consisting of kagome layers stacked along the z-axis with atoms either filling the geometric centers of the kagome lattice or embedded between the layers.In this topical review,we begin by introducing the fundamental properties of several kagome materials.To gain an in-depth understanding of the relationship between topology and correlation,we then discuss the complex phenomena observed in these systems.These include the simplest kagome metal T_(3)X,kagome intercalation metal T X,and the ternary compounds AT_(6)X_(6)and RT_(3)X_(5)(A=Li,Mg,Ca,or rare earth;T=V,Cr,Mn,Fe,Co,Ni;X=Sn,Ge;R=K,Rb,Cs).Finally,we provide a perspective on future experimental work in this field.

Electronic structure,elasticity,magnetism of Mn_(2)XIn(X=Fe,Co)full Heusler compounds under biaxial strain:First-principles calculations

The electronic structure,elasticity,and magnetic properties of the Mn_(2)XIn(X=Fe,Co)full-Heusler compounds are comprehensively investigated via first-principles calculations.The calculated elastic constants indicate that both Mn_(2)FeIn and Mn_(2)Co In possess ductility.At the optimal lattice constants,the magnetic moments are found to be 1.40μB/f.u.for Mn_(2)FeIn and 1.69μB/f.u.for Mn_(2)CoIn.Under the biaxial strain ranging from-2%to 5%,Mn_(2)FeIn demonstrates a remarkable variation in the spin polarization,spanning from-2%to 74%,positioning it as a promising candidate for applications in spintronic devices.Analysis of the electronic structure reveals that the change in spin polarization under strain is due to the shift of the spin-down states at the Fermi surface.Additionally,under biaxial strain,the magnetic anisotropy of Mn_(2)FeIn undergoes a transition of easy-axis direction.Utilizing second-order perturbation theory and electronic structure analysis,the variation in magnetic anisotropy with strain can be attributed to changes of d-orbital states near the Fermi surface.

Integration of wearable electronics and heart rate variability for human physical and mental well-being assessment

Heart rate variability(HRV)that can reflect the dynamic balance between the sympathetic nervous and parasympathetic nervous of human autonomic nervous system(ANS)has attracted considerable attention.However,traditional electrocardiogram(ECG)devices for HRV analysis are bulky,and hard wires are needed to attach measuring electrodes to the chest,resulting in the poor wearable experience during the long-term measurement.Compared with that,wearable electronics enabling continuously cardiac signals monitoring and HRV assessment provide a desirable and promising approach for helping subjects determine sleeping issues,cardiovascular diseases,or other threats to physical and mental well-being.Until now,significant progress and advances have been achieved in wearable electronics for HRV monitoring and applications for predicting human physical and mental well-being.In this review,the latest progress in the integration of wearable electronics and HRV analysis as well as practical applications in assessment of human physical and mental health are included.The commonly used methods and physiological signals for HRV analysis are briefly summarized.Furthermore,we highlighted the research on wearable electronics concerning HRV assessment and diverse applications such as stress estimation,drowsiness detection,etc.Lastly,the current limitations of the integrated wearable HRV system are concluded,and possible solutions in such a research direction are outlined.