Microwave awakening the n-π^(*) electronic transition in highly crystalline polymeric carbon nitride nanosheets for photocatalytic hydrogen generation

The n-π^(*) electronic transition in polymeric carbon nitride(PCN)can remarkably harvest visible light,which thus potentially promotes the photocatalytic hydrogen H2 generation.However,awaking the n-π^(*) lectronic transition has proven to be a grand challenge.Herein,we reported on the awakening of n-π^(*) electronic transition by microwave thermolysis of urea pellet,which yielded the PCN with absorption edge of 600 nm,near 140 nm red-shift from 460 nm of pristine PCN.The n-π^(*) electronic transition endows PCN with an increased photocata lytic H_(2) generation,with a highest H_(2) rate of 61.7μmol h^(-1) under visible light exposure,which is near 6 times higher than that by using the PCN from the thermolysis of urea pellets in an electric furnace(10.6μmol h^(-1)).Furthermore,the n-π^(*) transition in PCN leads to the longest wavelength of 535 nm that can initiate H2 generation,remarkably longer than the absorption edge of pristine PCN(460 nm).This work manifests the advantages of microwave sintering route to awaken the n-π^(*) electronic transition in PCN for an increased photocata lytic performance.

Two birds with one stone: Engineering polymeric carbon nitride with n-π^(*) electronic transition for extending light absorption and reducing charge recombination

The weak visible light harvesting and high charge recombination are two main problems that lead to a low photocatalytic H2 generation of polymeric carbon nitride(p-CN).To date,the approaches that are extensively invoked to address this problem mainly rely on heteroatom-doping and heterostructures,and it remains a grand challenge in regulating dopant-free p-CN for increasing H2 generation.Here,we report utilizing the inherent n-π^(*)electronic transition to simultaneously realize extended light absorption and reduced charge recombination on pCN nanosheets.Such n-π^(*)electronic transition yields a new absorption peak of 490 nm,which extends the light absorption edge of p-CN to approximately 590 nm.Meanwhile,as revealed by the photoluminescence(PL)spectra of p-CN at the single-particle level,the n-π*electronic transition gives rise to an almost quenched PL signal at room temperature,unravelling a dramatically reduced charge recombination.As a consequence,a remarkably improved photocatalytic performance is realized under visible light irradiation,with a H2 generation rate of 5553μmol g^(-1)·h^(-1),~12 times higher than that of pristine p-CN(460μmol·g^(-1)·h^(-1))in the absence of the n-π^(*)transition.This work illustrates the highlights of using the inherent n-π^(*)electronic transition to improve the photocatalytic performance of dopant-free carbon nitrides.

THE LINEAR CORRELATIONS BETWEEN ELECTRONIC TRANSITION ENERGY AND HAMMETT CONSTANTS FOR THE SUBSTITUTED PORPHYRIN-LIKE MACROCYCLE

The properties of absorption spectra are presented and the linear correlations of Hammett constants with the 0-0 transition energy(E_(o,o))of S_←S_o, and the ratios of oscillator strength(f/f)are used to probe the interactions betwee π-electron of aromatic maerocycles or metal ion of complexes with the sub- stituents on β-position of benzene ring for porphyrin-like maerocyclic compounds.

Variation of electronic transition moment versus internuclear distance for NO (A^2∑→X^2Ⅱ) transition

Two-photon laser-induced fluorescence spectrum (TP-LIF) of NO is obtained with a Nd:YAG pumped optical parametric generator and amplifier as radiation source. Spectral intensity distribution shows that the electronic transition moment for NO (A2 X2II) transition varies significantly with inter-nuclear distance. The variation relationship of the electronic transition moment versus inter-nuclear distance is deduced with polyminal fit procedure. The spontaneous radiative coefficients for NO (A2X2II) transition from v' = 0,1 are obtained by combing this transition moment variation with the measurements of spontaneous radiative lifetime.

A Precise Description of the Electronic Structures and Spin-Allowed Transition Properties of PF and Its Cation:All-Electron Configuration-Interaction Investigations Including Relativistic Effect

The electronic structures of PF and PF＋ are calculated with the high-level configuration interaction method. To improve the precision of calculations, the spin-orbit coupling effect, the scalar relativistic effect, and the Davidson correction（q-Q） are also considered. The spectroscopic parameters of bound states are derived by the electronic structures of PF and PF＋, which are in good accordance with the measurements. The transition dipole moments of spin-allowed transitions are evaluated, and the radiative lifetimes of several A S states of PF and PF＋ are obtained.

Electronic Structure Reconstruction across the Antiferromagnetic Transition in TaFe1.23Te3 Spin Ladder

Employing the angle-resolved photoemission spectroscopy, we study the electronic structure of TaFe1.23Te3, a two-leg spin ladder compound with a novel antiferromagnetic ground state. Quasi-two-dimensional （2D） Fermi surface is observed, with sizable inter-ladder hopping. Moreover, instead of observing an energy gap at the Fermi surface in the antiferromagnetic state, we observe the shifts of various bands. Combining these observations with density-functional-theory calculations, we propose that the large scale reconstruction of the electronic structure, caused by the interactions between the coexisting itinerant electrons and local moments, is most likely the driving force of the magnetic transition. Thus TaFe1.23Te3 serves as a simpler platform that contains similar ingredients to the parent compounds of iron-based superconductors.

In situ electronic structural study of VO_2 thin film across the metal–insulator transition

The in situ valence band photoemission spectrum （PES） and X-ray absorption spectrum （XAS） at V LⅡ-LⅢ edges of the VO2 thin film, which is prepared by pulsed laser deposition, are measured across the metal–insulator transition （MIT） temperature （TMIT=67 ℃）. The spectra show evidence for changes in the electronic structure depending on temperature. Across the TMIT, pure V 3d characteristic d‖ and O 2p-V 3d hybridization characteristic πpd, σpd bands vary in binding energy position and density of state distributions. The XAS reveals a temperature-dependent reversible energy shift at the V LⅢ-edge. The PES and XAS results imply a synergetic energy position shift of occupied valence bands and unoccupied conduction band states across the phase transition. A joint inspection of the PES and XAS results shows that the MIT is not a one-step process, instead it is a process in which a semiconductor phase appears as an intermediate state. The final metallic phase from insulating state is reached through insulator–semiconductor, semiconductor–metal processes, and vice versa. The conventional MIT at around the TMIT=67 ℃ is actually a semiconductor–insulator transformation point.

Unveiling the pressure-driven metal–semiconductor–metal transition in the doped TiS_(2)

Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_(1)2_(1)2_(1).Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.

Recent Developments of Transition Metal Compounds-Carbon Hybrid Electrodes for High Energy/Power Supercapacitors

Due to their rapid power delivery,fast charging,and long cycle life,supercapacitors have become an important energy storage technology recently.However,to meet the continuously increasing demands in the fields of portable electronics,transportation,and future robotic technologies,supercapacitors with higher energy densities without sacrificing high power densities and cycle stabilities are still challenged.Transition metal compounds(TMCs)possessing high theoretical capacitance are always used as electrode materials to improve the energy densities of supercapacitors.However,the power densities and cycle lives of such TMCs-based electrodes are still inferior due to their low intrinsic conductivity and large volume expansion during the charge/discharge process,which greatly impede their large-scale applications.Most recently,the ideal integrating of TMCs and conductive carbon skeletons is considered as an effective solution to solve the above challenges.Herein,we summarize the recent developments of TMCs/carbon hybrid electrodes which exhibit both high energy/power densities from the aspects of structural design strategies,including conductive carbon skeleton,interface engineering,and electronic structure.Furthermore,the remaining challenges and future perspectives are also highlighted so as to provide strategies for the high energy/power TMCs/carbon-based supercapacitors.

Magnetic transition behavior of perovskite manganites Nd0.5Sr0.3Ca0.2MnO3 polycrystalline

A polycrystalline sample Ndo.5Sro.3Cao.2MnO3 is prepared by the conventional solid state reaction method. The structure and magnetic properties are investigated with x-ray diffraction （XRD） patterns, a superconducting quantum in- terference device （SQUID）, and electron spin resonance （ESR）. The sample is in single phase with the space group Pbnm symmetry. With the decrease of temperature, Ndo.sSro.3Cao.2MnO3 undergoes three magnetic transitions： ferromagnetic transition at Tc ≈ 210 K, charge-ordering at Tco ≈ 175 K, and antiferromagnetic transition at TN = 155 K. In addition, the activation energy Ea ≈ 52.78 meV can be extracted by curve fitting.

Electron Transition of Eu^(2+) and Energy Transfer in Crystals BaFX:Eu^(2+),Eu^(3+) (X=Cl,Br)

In crystals BaFX:Eu^(2+)(X=Cl,Br).there exists configuration interaction between 4f^65d and 4f^65s ex- cited state of Eu^(2+)ion.and it results in the change of relative intensities of d-f and f-f transition.The transition ~S_-_2→4f^65d-6s is observed.The variation of F/X atomic ratio between 110/90 and 90/110 does not obvi- ously influence the luminescence of BaFX:Eu^(2-).There is energy transfer between Eu^(2+)(f-f)and Eu^(3+)which coexists in the matrices.

Effect and Mechanism Analysis of Solvent on the Electron Transition of Fluoroquinolones Based on Quantum Chemical Calculation

Ciprofloxacin（CIP）, moxifoxacin（MOX） and enrofloxacin（ENR） were selected as typical fluoroquinolones（FQs） to analyze the excitation-enhancing effect and mechanism of solvents on FQs＇ electron transition based on quantum chemical calculations. The UV spectra of three FQs in gas and five different solvents（water, cyclohexane, dimethylsulfoxide, methanol, acetone） were calculated using Gaussian 09 software. The transition mechanisms of FQs＇ main electron transitions were analyzed by natural bond orbital（NBO） theory, and the solvent effect on each electron transition was assessed qualitatively and quantitatively by sensitivity analysis and an established index system. The excitation enhancing mechanism of solvent on electron transitions of FQs was analyzed from the view of photo-induced reactions between solvent and FQs molecules. The results show that there are two main transitions located in the spectrum ranges of 300~380 and 240~300 nm for each FQ in any medium, which are assigned as n →π＊ and π→π＊ electron transitions, respectively. By comparison, the n →π＊ transition is more sensitive to solvent because of the energy transfer between solvent molecules and FQs, but the solvent effect on the π→π＊ transition is stronger than on the n →π＊ transition. The sequence of affected extent of solvent effect on electron transition was CIP 〉 MOX 〉 ENR, and the sequence of solvent effect was water 〉 DMSO 〉 methanol 〉 acetone 〉 cyclohexane（stronger solvent effect with increasing the dielectric constant of solvent）. From the view of photo-induced reactions, the reaction between FQs＊T1 and solvent＊T1 has the decisive regulatory effect on the n →π＊ transition of FQs in solvent, and the reaction between FQsS0 and solvent＊TI has an enhancing effect on the π→π＊ transition.

Scheme for the excitation of thorium-229 nuclei based on electronic bridge excitation

Thorium-229 possesses the lowest first nuclear excited state,with an energy of approximately 8 eV.The extremely narrow linewidth of the first nuclear excited state,with an uncertainty of 53 THz,prevents direct laser excitation and realization of the nuclear clock.We present a proposal using the Coulomb crystal of a linear chain formed by229Th^(3+)ions,where the nuclei of229Th3+ions in the ion trap are excited by the electronic bridge(EB)process.The 7 P1∕2state of the thorium-229 nuclear ground state is chosen for EB excitation.Using the two-level optical Bloch equation under experimental conditions,we calculate that 2 out of 36 prepared thorium ions in the Coulomb crystal can be excited to the first nuclear excited state,and it takes approximately 2 h to scan over an uncertainty of 0.22 eV.Taking advantage of the transition enhancement of EB and the long stability of the Coulomb crystal,the energy uncertainty of the first excited state can be limited to the order of 1 GHz.

Giant Volume Magnetostriction Caused by Itinerant Electron Metamagnetic Transition and Pronounced Invar Effects in La(Fe_xSi_(1-x))_(13) Compounds

A first-order itinerant electron metamagnetic (IEM) transition above the Curie temperature Tc for ferromagnetic La(Fe_xSi_1-x)13 compounds has been confirmed by applying magnetic field. The volume change just above T_C for x=0.88 is huge of about 1.5%, which is caused by a large magnetic moment induced by the IEM transition. These compounds have a possibility for practical applications as giant magnetostrictive materials. Pronounced Invar effects bring about a negative thermal expansion below TC, closely correlated with the negative mode-mode coupling among spin fluctuations.

Quantitative Characterization and Elastic Properties of Interfacial Transition Zone around Coarse Aggregate in Concrete

Backscattered electron images（BSE） obtained by scanning electron microscope was used to quantitatively characterize the microstructure of interfacial transition zone（ITZ） in concrete. Influences of aggregate size（5, 10, 20, and 30 mm）, water to cement ratio（0.23, 0.35 and 0.53） and curing time（from 3d to 90d） on the microstructure of interfacial transition zone between coarse aggregate and bulk cement matrix were investigated. The volume percentage of detectable porosity and unhydrated cement in ITZ was quantitatively analyzed and compared with that in the matrix of various concretes. Nanoindentation technology was applied to obtain the elastic properties of ITZ and matrix, and the elastic modulus of concrete was then calculated based on the Lu ＆ Torquato model and self-consistence scheme by using the ITZ thickness and elastic modulus obtained from this investigation. The experimental results demonstrated that the microstructure and thickness of ITZ in concrete vary with a variety of factors, like aggregate size, water to cement ratio and curing time. The relative low elastic properties of ITZ should be paid attention to, especially for early age concrete.

Emission Intensity in the Hydrogen Atom Calculated from a Non-Probabilistic Approach to the Electron Transitions

Quantum aspects of the Joule-Lenz law for the transmission of energy allowed us to calculate the time rate of energy transitions between the quantum states of the hydrogen atom in a fully non-probabilistic way. The calculation has been extended to all transitions between p and s states having main quantum numbers not exceeding 6. An evident similarity between the intensity pattern obtained from the Joule-Lenz law and the corresponding quantum-mechanical transition pro-babilities has been shown.

Time Intervals of the Electron Transitions between the Energy States in the Hydrogen Atom Calculated in a Non-Probabilistic Way

Definitions of the mechanical parameters entering the Bohr model of the hydrogen atom allowed us to calculate the time intervals connected with the electron transitions between the nearest-neighbouring energy levels in the atom. This is done in a strictly non-probabilistic way. The time results are compared with those derived earlier on the basis of the classical Joule-Lenz law for the energy emission adapted to the case of the electron transfer in the quantum systems. A similar formalism has been next applied to the harmonic oscillator and a particle moving in the one-dimensional potential box.

ABSORPTION SPECTRA OF 4f ELECTRON TRANSITIONS IN THE SYSTEM OF NEODYMIUMSEMIXYLENOL ORANGE-CETYLPYRIDINIUM CHLORIDE

In this paper the absorption spectra of Nd-SXO-CPC complex by 4f electron transitions have been studied by zero-order and fourth-order derivative spectrophotome-try. The molar absorptivity is 2.6×10~3 1.mol^(-1).cm^(-1) at 585 nm, the fourth-order derivative molar absorptivity is 1.4×10~4 1.mol^(-1).cm^(-1) at 584.5(-) and 587(+) nm. They are 300 times and 1600 times greater than those of the chloride, respectively.

ABSORPTION SPECTRA OF 4f ELECTRON TRANSITIONS OF NEODYMIUM COMPLEX WITH 8-HYDROXYQUINOLINE AND OCTYLPHENOL POLY(ETHYLENEGLYCOL)ETHER

In this paper the absorption spectra of 4f electron transitions of the neodymlum complex with 8-hydroxyquinoline and octylphenol poly(ethyleneglycol)ether have been studied. The marked intensification of the band at low octylphenol poly(ethyleneglycol)ether concentration is found normally at 575 nm, and its resolution into three sharp bands centering at 572, 580 and 584 nm. The absorbances of the absorption maxima are 3.5 (at 572 nm), 7.2 (at 580 nm) and 10.2 (at 584 nm) times greater than that of the chloride.

Magnetic Phase Transition and Magnetic Entropy Change in La_(0.8)Pr_(0.2)Fe_(11.4)Si_(1.6) Compound

The magnetic properties and the phase transformation of the partial substitution of Pr for La in LaFe11.4Si1.6 have been investigated by the means of X-ray diffraction (XRD) and vibrating sample magnetic (VSM). The results indicated that the single phase NaZn13-type cubic structure is stabilized for the compound La0.8Pr0.2Fe11.4Si1.6 and large values of the isothermal magnetic entropy change SM around the curie temperature TC～194 K in relative low magnetic fields. The maximum value︱SM︱max～37.07 J/kg·K-1 under a field of 1.5 T. Such large MCEs are attributed to the sharp change of the magnetization at the Curie temperature, the field-induced IEM transition and a strong temperature dependence of the critical field BC.