配对赝能隙的观测与定量刻画

1956年,库珀发现在极低温下,自旋方向相反的费米子在吸引相互作用下会束缚在一起,形成著名的库珀对[1]。这一概念的提出为理解超导现象奠定了基础。1957年,巴丁、库珀和施里弗共同提出了BCS理论,解释了常规超导的机制[2]:在极低温下,电声子耦合提供了电子间的弱吸引相互作用,使其配对形成库珀对。由于库珀对是玻色子,它们在低温下又会发生玻色-爱因斯坦凝聚,从而产生超导能隙.

Machine learning molecular dynamics simulations of liquid methanol

As the simplest hydrogen-bonded alcohol,liquid methanol has attracted intensive experimental and theoretical interest.However,theoretical investigations on this system have primarily relied on empirical intermolecular force fields or ab initio molecular dynamics with semilocal density functionals.Inspired by recent studies on bulk water using increasingly accurate machine learning force fields,we report a new machine learning force field for liquid methanol with a hybrid functional revPBE0 plus dispersion correction.Molecular dynamics simulations on this machine learning force field are orders of magnitude faster than ab initio molecular dynamics simulations,yielding the radial distribution functions,selfdiffusion coefficients,and hydrogen bond network properties with very small statistical errors.The resulting structural and dynamical properties are compared well with the experimental data,demonstrating the superior accuracy of this machine learning force field.This work represents a successful step toward a first-principles description of this benchmark system and showcases the general applicability of the machine learning force field in studying liquid systems.

Nickel catalysts with asymmetric steric hindrance for ethylene polymerization

α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.

Charge-balanced codoping enables exceeding doping limit and ultralow thermal conductivity

Materials with low thermal conductivity are applied extensively in energy management,and breaking the amorphous limits of thermal conductivity to solids has attracted widespread attention from scientists.Doping is a common strategy for achieving low thermal conductivity that can offer abundant scattering centers in which heavier dopants always result in lower phonon group velocities and lower thermal conductivities.However,the amount of equivalent heavyatom single dopant available is limited.Unfortunately,nonequivalent heavy dopants have finite solubility because of charge imbalance.Here,we propose a charge balance strategy for SnS by substituting Sn2+with Ag^(+)and heavy Bi^(3+),improving the doping limit of Ag from 2%to 3%.Ag and Bi codoping increases the point defect concentration and introduces abundant boundaries simultaneously,scattering the phonons at both the atomic scale and nanoscale.The thermal conductivity of Ag0.03Bi0.03Sn0.94S decreased to 0.535 W·m^(−1)·K^(−1)at room temperature and 0.388 W·m^(−1)·K^(−1)at 275°C,which is below the amorphous limit of 0.450 W·m^(−1)·K^(−1)for SnS.This strategy offers a simple way to enhance the doping limit and achieve ultralow thermal conductivity in solids below the amorphous limit without precise structural modification.

Freestanding oxide membranes:synthesis,tunable physical properties,and functional devices

The study of oxide heteroepitaxy has been hindered by the issues of misfit strain and substrate clamping,which impede both the optimization of performance and the acquisition of a fundamental understanding of oxide systems.Recently,however,the development of freestanding oxide membranes has provided a plausible solution to these substrate limitations.Single-crystalline functional oxide films can be released from their substrates without incurring significant damage and can subsequently be transferred to any substrate of choice.This paper discusses recent advancements in the fabrication,adjustable physical properties,and various applications of freestanding oxide perovskite films.First,we present the primary strategies employed for the synthesis and transfer of these freestanding perovskite thin films.Second,we explore the main functionalities observed in freestanding perovskite oxide thin films,with special attention to the tunable functionalities and physical properties of these freestanding perovskite membranes under varying strain states.Next,we encapsulate three representative devices based on freestanding oxide films.Overall,this review highlights the potential of freestanding oxide films for the study of novel functionalities and flexible electronics.

Large and nonlinear electric field response in a two-dimensional ferroelectric Rashba material

The achievement of electrical spin control is highly desirable.One promising strategy involves electrically mod-ulating the Rashba spin orbital coupling effect in materials.A semiconductor with high sensitivity in its Rashba constant to external electric fields holds great potential for short channel lengths in spin field-effect transistors,which is crucial for preserving spin coherence and enhancing integration density.Hence,two-dimensional(2D)Rashba semiconductors with large Rashba constants and significant electric field responses are highly desirable.Herein,by employing first-principles calculations,we design a thermodynamically stable 2D Rashba semiconductor,YSbTe_(3),which possesses an indirect band gap of 1.04 eV,a large Rashba constant of 1.54 eV·Åand a strong electric field response of up to 4.80 e·Å^(2).In particular,the Rashba constant dependence on the electric field shows an unusual nonlinear relationship.At the same time,YSbTe_(3)has been identified as a 2D ferroelectric material with a moderate polarization switching energy barrier(~0.33 eV per formula).By changing the electric polarization direction,the Rashba spin texture of YSbTe_(3)can be reversed.These out-standing properties make the ferroelectric Rashba semiconductor YSbTe_(3)quite promising for spintronic applications.

Synergistic effect of heterogeneous single atoms and clusters for improved catalytic performance

Electrocatalytic water splitting provides an efficient method for the production of hydrogen.In electrocatalytic water splitting,the oxygen evolution reaction(OER)involves a kinetically sluggish four-electron transfer process,which limits the efficiency of electrocatalytic water splitting.Therefore,it is urgent to develop highly active OER catalysts to accelerate reaction kinetics.Coupling single atoms and clusters in one system is an innovative approach for developing efficient catalysts that can synergistically optimize the adsorption and configuration of intermediates and improve catalytic activity.However,research in this area is still scarce.Herein,we constructed a heterogeneous single-atom cluster system by anchoring Ir single atoms and Co clusters on the surface of Ni(OH)_(2)nanosheets.Ir single atoms and Co clusters synergistically improved the catalytic activity toward the OER.Specifically,Co_(n)Ir_(1)/Ni(OH)_(2)required an overpotential of 255 mV at a current density of 10 mA·cm^(−2),which was 60 mV and 67 mV lower than those of Co_(n)/Ni(OH)_(2)and Ir1/Ni(OH)_(2),respectively.The turnover frequency of Co_(n)Ir_(1)/Ni(OH)_(2)was 0.49 s^(−1),which was 4.9 times greater than that of Co_(n)/Ni(OH)_(2)at an overpotential of 300 mV.

Electronic Transport Properties of Spin-Crossover Magnet Fe（Ⅱ）-N4S2 Complexes

Spin-crossover （SCO） magnets can act as one of the most possible building blocks in molec- ular spintronics due to their magnetic bistability between the high-spin （HS） and low-spin （LS） states. Here, the electronic structures and transport properties through SCO magnet Fe（II）-N4S2 complexes sandwiched between gold electrodes are explored by performing exten- sive density functional theory calculations combined with non-equilibrium Green＇s function formalism. The optimized Fe-N and Fe-S distances and predicted magnetic moment of the SCO magnet Fe（II）-N4S2 complexes agree well with the experimental results. The reversed spin transition between the HS and LS states can be realized by visible light irradiation according to the estimated SCO energy barriers. Based on the obtained transport results, we observe nearly perfect spin-filtering effect in this SCO magnet Fe（II）-N4S2 junction with the HS state, and the corresponding current under small bias voltage is mainly contributed by the spin-down electrons, which is obviously larger than that of the LS case. Clearly, these theoretical findings suggest that SCO magnet Fe（II）-N4S2 complexes hold potential applications in molecular spintronies.

Detection of Tetracycline Antibiotics in Water by Dispersive Micro-solid Phase Extraction using Fe_(3)O_(4)@[Cu_(3)(btc)_(2)]Magnetic Composite Combined with Liquid Chromatography-Tandem Mass Spectrometry

Residues of tetracycline antibiotics(TCs) in environments may be harmful to human.Due to their high polarities,it is extremely challenging to efficiently enrich TCs with low concentrations in natural waters for analysis.In this work,a magnetic metal-organic framework Fe_(3)O_(4)@[Cu_(3)(btc)_(2)]was synthesized and applied as a dispersive micro-solid phase extraction adsorbent for TCs enrichment.Effects of dispersive micro-solid phase extraction conditions including extraction time,solution p H,and elution solvent on the extraction efficiencies of TCs were investigated.Results show that TCs could be enriched efficiently by Fe_(3)O_(4)@[Cu_(3)(btc)_(2)],and electrostatic interaction between TCs and Fe_(3)O_(4)@[Cu_(3)(btc)_(2)]dominated this process.Combined with liquid chromatography-tandem mass spectrometry,four TCs residues (oxytetracycline,tetracycline,chlortetracycline,and doxycycline) in natural waters were determined.The detection limits (LOD,S/N=3) of the four antibiotics were 0.01-0.02μg/L,and the limits of quantitation (LOQ,S/N=10)were 0.04-0.07μg/L.The recoveries obtained from river water and aquaculture water spiked with three TCs concentration levels ranged from 70.3%to 96.5%with relative standard deviations of 3.8%-12.8%.Results indicate that the magnetic metal-organic framework based dispersive micro-solid phase extraction is simple,rapid and high-loading for antibiotics enrichment from water,which further expand the practical application of metal-organic frameworks in sample pretreatment for environmental pollutant analysis.

Machine-Learning Adsorption on Binary Alloy Surfaces for Catalyst Screening

Over the last few years, machine learning is gradually becoming an essential approach for the investigation of heterogeneous catalysis. As one of the important catalysts, binary alloys have attracted extensive attention for the screening of bifunctional catalysts. Here we present a holistic framework for machine learning approach to rapidly predict adsorption energies on the surfaces of metals and binary alloys. We evaluate different machine-learning methods to understand their applicability to the problem and combine a tree-ensemble method with a compressed-sensing method to construct decision trees for about 60000 adsorption data.Compared to linear scaling relations, our approach enables to make more accurate predictions lowering predictive root-mean-square error by a factor of two and more general to predict adsorption energies of various adsorbates on thousands of binary alloys surfaces, thus paving the way for the discovery of novel bimetallic catalysts.

Cavity-Enhanced Saturation Spectroscopy of Molecules with sub-k Hz Accuracy

Saturation spectroscopy is frequently used to obtain sub-Doppler measurement of atomic and molecular transitions. Optical resonant cavities can be used to enhance the effective absorption path length, and the laser power inside the cavity as well to saturate very weak ro-vibrational transitions of molecules. Three different cavity-enhanced methods, cavity enhanced absorption spectroscopy, cavity ring-down spectroscopy, and noise-immune cavity enhanced optical heterodyne molecular spectroscopy (NICE-OHMS), were compared by measuring the Lamb dip of a C2H2 line at 1.4 μm using a cavity with a finesse of 120000. The center of the line was determined by different cavity-enhanced methods, each giving a sub-kHz (δv/v≈10-12) statistical uncertainty. The sensitivity and precision of different methods were analyzed and compared. As demonstrated in this study, the NICE-OHMS method is the most sensitive one, but more investigation on the systematic uncertainty is necessary before its application in metrology studies toward a sub-kHz accuracy.

Bias-Polarity Dependent Electroluminescence from a Single Platinum Phthalocyanine Molecule

By using scanning tunneling microscope induced luminescence(STML)technique,we investigate systematically the bias-polarity dependent electroluminescence behavior of a single platinum phthalocyanine(PtPc)molecule and the electron excitation mechanisms behind.The molecule is found to emit light at both bias polarities but with different emission energies.At negative excitation bias,only the fluorescence at 637 nm is observed,which originates from the LUMOtHOMO transition of the neutral PtPc molecule and exhibits stepwise-like increase in emission intensities over three different excitation-voltage regions.Strong fluorescence in region(I)is excited by the carrier injection mechanism with holes injected into the HOMO state first;moderate fluorescence in region(II)is excited by the inelastic electron scattering mechanism;and weak fluorescence in region(III)is associated with an up-conversion process and excited by a combined carrier injection and inelastic electron scattering mechanism involving a spintriplet relay state.At positive excitation bias,more-than-one emission peaks are observed and the excitation and emission mechanisms become complicated.The sharp moleculespecific emission peak at〜911 nm is attributed to the anionic emission of PtPc-originated from the LUMO+1 tLUMO transition,whose excitation is dominated by a carrier injection mechanism with electrons first injected into the LUMO+1 or higher-lying empty orbitals.

Phosphorene-Based van der Waals Heterojunction for Solar Water Splitting

As a clean and renewable future energy source, hydrogen fuel can be produced via solar water splitting. Two-dimensional (2D) black phosphorene (black-P) can harvest visible light due to the desirable band gap, which promises it as a metal-free photocatalyst. However, black-P can be only used to produce hydrogen since the oxidation potential of water locates lower than the position of the valence band maximum. To improve the photocatalytic performance of black-P, here, using black-P and blue phosphorene (blue-P) monolayers, we propose a 2D van der Waals (vdW) heterojunction. Theoretical results, including the band structures, density of states, Bader charge population, charge density di erence, and optical absorption spectra, clearly reveal that the visible light absorption ability is obviously improved, and the band edge alignment of the proposed vdW heterojunction displays a typical type-II feature to effectively separate the photogenerated carriers. At the same time, the built-in interfacial electric field prevents the electron-hole recombination. These predictions suggest that the examined phosphorene-based vdW heterojunction is an efficient photocatalyst for solar water splitting.

Single Pt Atoms Supported on Oxidized Graphene as a Promising Catalyst for Hydrolysis of Ammonia Borane

Based on density functional theory calculations,the full hydrolysis of per NH3BH3 molecule to produce three hydrogen molecules on single Pt atoms supported on oxidized graphene(Pt1/Gr-O)is investigated.It is suggested that the first hydrogen molecule is produced by the combination of two hydrogen atoms from two successive B-H bonds breaking.Then one H2O molecule attacks the left*BHNH3 group(*represents adsorbed state)to form*BH(H2O)NH3 and the elongated O-H bond is easily broken to produce*BH(OH)NH3.The second H2O molecule attacks*BH(OH)NH3 to form*BH(OH)(H2O)NH3 and the breaking of O-H bond pointing to the plane of Pt1/Gr-O results in the desorption of BH(OH)2NH3.The second hydrogen molecule is produced from two hydrogen atoms coming from two H2O molecules and Pt1/Gr-O is recovered after the releasing of hydrogen molecule.The third hydrogen molecule is generated by the further hydrolysis of BH(OH)2NH3 in water solution.The rate-limiting step of the whole process is the combination of one H2O molecule and*BHNH3 with an energy barrier of 16.1 kcal/mol.Thus,Pt1/Gr-O is suggested to be a promising catalyst for hydrolysis of NH3BH3 at room temperature.

A Simple,Compact and Rigid Scanning Tunneling Microscope

We present a homebuilt scanning tunneling microscope(STM)which employs an inner-wall polished sapphire guiding tube as a rail for the scanner to form a short tip-sample mechanical loop.The scanner is mounted on a square rod which is housed in the guiding tube and held by a spring strip.The stiff sapphire guiding tube allows the STM body to be made in a simple,compact and rigid form.Also the material of sapphire improves the thermal stability of the STM for its good thermal conductivity.To demonstrate the performance of the STM,high quality atomic-resolution STM images of high oriented pyrolytic graphite were given.

Theoretical Study of Adsorption and Dehydrogenation of C2H4 on Cu（410）

Adsorption and dehydrogenation of ethylene on Cu（410） surface are investigated with first- principles calculations and micro-kinetics analysis. Ethylene dehydrogenation is found to start from the most stable π-bonded state instead of the previously proposed di〈r-bonded state. Our vibrational frequencies calculations verify the π-bonded adsorption at step sites at low coverage and low surface temperature and di-σ-bonded ethylene on C-C dimer （C2H4- CC） is proposed to be the species contributing to the vibrational peaks experimentally observed at high coverage at 193 K. The presence of C2H4-CC indicates that the dehydro- genation of ethylene on Cu（410） can proceed at temperature as low as 193 K.

Computational Characterization of Nanosystems

Nanosystems play an important role in many applications.Due to their complexity,it is challenging to accurately characterize their structure and properties.An important means to reach such a goal is computational simulation,which is grounded on ab initio electronic structure calculations.Low scaling and accurate electronic-structure algorithms have been developed in recent years.Especially,the efficiency of hybrid density functional calculations for periodic systems has been significantly improved.With electronic structure information,simulation methods can be developed to directly obtain experimentally comparable data.For example,scanning tunneling microscopy images can be effectively simulated with advanced algorithms.When the system we are interested in is strongly coupled to environment,such as the Kondo effect,solving the hierarchical equations of motion turns out to be an effective way of computational characterization.Furthermore,the first principles simulation on the excited state dynamics rapidly emerges in recent years,and nonadiabatic molecular dynamics method plays an important role.For nanosystem involved chemical processes,such as graphene growth,multiscale simulation methods should be developed to characterize their atomic details.In this review,we review some recent progresses in methodology development for computational characterization of nanosystems.Advanced algorithms and software are essential for us to better understand of the nanoworld.

Quantum Entanglement of Parallel-Coupled Double Quantum Dots:a Theoretical Study Using the Hierarchical Equations of Motion Approach

Quantum dots comprise a type of quantum impurity system. The entanglement and co- herence of quantum states are significantly influenced by the strong electron-electron interactions among impurities and their dissipative coupling with the surrounding environment. Competition between many-body effects and transfer couplings plays an important role in determining the entanglement among localized impurity spins. In this work, we employ the hierarchical-equations-of-rnotion approach to explore the entanglement of a strongly correlated double quantum dots system. The relation between the total system entropy and those of subsystems is also investigated.

Role of Reduced Defects for Coupling Reactions of Acetaldehyde on Anatase TiO2（001）-（1×4） Surface

The chemistry of acetaldehyde (CH3CHO) adsorbed on the anatase TiO2(001)-(1×4) surface has been investigated by temperature-programmed desorption (TPD) method. Our experimental results provide the direct evidence that the perfect lattice sites on the anatase TiO2(001)-(1×4) surface are quite inert for the reaction of CH3CHO, but the reduced defect sites on the surface are active for the thermally driven reductive carbon-carbon coupling reactions of CH3CHO to produce 2-butanone and butene. We propose that the coupling reactions of CH3CHO on the anatase TiO2(001)-(1×4) surface should undergo through the adsorption of paired CH3CHO molecules at the reduced defect sites, since the existing reduced Ti pairs provide the suitable adsorption sites.

Boosting fuel cell catalysis by surface doping of W on Pd nanocubes

The development of active and durable non-Pt electrocatalysts with well-defined microstructure is of great importance to both fuel cell applications and fundamental understanding.Herein,we report a surface-doping process to prepare well-defined W-doped Pd nanocubes with a tunable atomic percent of W from 0 to 1.5%by using the Pd nanocubes as seeds.The obtained 1.2%W-doped Pd nanocubes/C exhibited greatly enhanced electrocatalytic performance toward oxygen reduction reaction in alkaline media,presenting an enhancement factor of 4.7 in specific activity and 2.5 in mass activity compared to the activity of a commercial Pt/C catalyst.The downshift of the d-band center due to a negative charge transfer from W to Pd intrinsically accounts for such improvement in activity by weakening the adsorption of reaction intermediates.Also,the 1.2%W-doped Pd nanocubes/C showed superior catalytic properties for the ethanol oxidation reaction,showing great potential for serving as a bifunctional electrocatalyst in fuel cells.