含空位二维六角氮化硼电子和磁性质的密度泛函研究

基于密度泛函理论的第一性原理计算, 研究了含B原子空位(V_B), N原子空位(V_N), 以及含B–N键空位 (V_B+N)缺陷的二维氮化硼(h-BN)的电子和磁性质. 在微观结构上, V_B体系表现为在空位附近的N原子重构成等腰三角形, V_N体系靠近空穴的B 原子形成等边三角形, V_B+N体系靠近空穴处的B和N原子在h-BN平面上重构为梯形. 三种空位缺陷都使h-BN的带隙类型从直接带隙转变为间接带隙. V_B体系的总磁矩为1.0 μ_B, 磁矩全部由N原子贡献. 其中空穴周围的三个N原子磁矩方向不完全一致, 存在着铁磁性和反铁磁性两种耦合方式. 对于V_N 体系, 整个晶胞内的总磁矩也为1.0 μ_B, 磁矩在空穴周围区域呈现一定的分布. 关键词： 二维h-BN 空位 电子结构 磁性     

The first-principle calculation of structures and defect energies in tetragonal PbTiO3

The first-principle calculation had been adopted to investigate various neutral vacancies and vacancy pairs under seven thermodynamic conditions in bulk PbTiO₃. The electronic structures, atomic relaxations, and formation energies of vacancies were obtained. Depending on the thermodynamic condition, the main and stable defects are different. It was found that V_O is the main defect under the reducing condition, whereas V_Pb becomes dominating under the oxidizing condition. The Pb-O vacancy pair forms more easily than the isolated vacancies under certain thermodynamic condition. Due to the introducing of vacancies, the acceptorlike levels and donorlike levels appear in the cases of the cation and anion vacancies, respectively.     

Study of cation tracer diffusion in NaF

Cation tracer diffusion coefficients were measured in pure NaF crystals in the intrinsic ionic conductivity range (876–970 °C). The results can be rationalized satisfactorily in terms of contributions to the observed Na tracer diffusivities arising from both free vacancies and neutral vacancy pairs, the latter contribution amounting to about 53 per cent of the total Na diffusion at the highest measuring temperature. The best-fit defect parameters derived in an earlier conductivity study [21] from this laboratory on similar NaF crystals give for the free vacancy contribution D_v^*(Na) = 4·25 exp (?2·21 eV/kT) cm²s^?1. A combination of these D_v^*(Na) values with the present diffusion data yields for the vacancy-pair contribution D_p^*(Na) = 1·15 × 10⁸exp (?4·04 eV/kT) cm²s^?1. Comparison of the present findings with published values of the anion tracer diffusion coefficient in NaF showed that D_p^* (F) is 2·3 to 4·4 times larger than D_p^*(Na) over the temperature range of our observations, the difference between the two contributions increasing with decreasing temperature. When approximate account is taken of the temperature-dependence of the two pair correlation factors, this last result indicates that the anion jumps into the vacancy pair occur with a higher frequency, and increasingly so at lower temperatures, than do those involving the cations.     

Local structure and lattice dynamics of alkali halide crystals with an anion vacancy

The local structure and vibrations in the region of an anion vacancy are studied using the pair interionic potentials within the shell model for crystals Me ⁺Cl^? (Me ⁺ = Rb⁺, K⁺, Na⁺). The pair potentials are derived from first-principles calculations of different clusters by the Hartree-Fock-Roothaan method with the one-electron states constructed in the form of molecular orbitals as linear combinations of atomic orbitals (MO LCAO). The calculations are performed with the GAMESS program package (US). The correlation corrections are included in the calculations. The validity of the model parameters is verified by comparing the calculated with experimental structural and dynamic properties of ideal alkali halide crystals.     

Observation of vacancy defect migration in the cation sublattice of complex oxides by 18O tracer experiments

We report on 18O tracer diffusion experiments and model calculations for the study of cation vacancy migration in oxide crystals. The model takes advantage of the electrostatic coupling forces between anion and cation defects that allow the evolution of the cation vacancy profile to be observed by anion tracer experiments. Applied to SrTiO3, the ambipolar diffusion of strontium vacancies with H(A)=3.5 eV was found to be the dominant reequilibration mechanism of the cation sublattice. This result is in contrast to earlier studies proposing the formation of SrO intergrowth phases.     

A first-principles study of the magnetic properties in boron-doped ZnO

First-principles calculations based on density functional theory are performed to study the origin of ferromagnetism in boron-doped ZnO. It is found that boron atoms tend to reside at Zn sites. The induced Zn vacancy is a key factor for ferromagnetism in Zn1-xBxO (0相似文献   

光致变色天然白色方钠石宝石学和光谱学特征探究

方钠石为似长石类矿物,常作为无机光致变色材料广泛应用于建筑、照明和放射量测定等领域。高品质方钠石宝石以其迷人的光致变色效应为大众熟知,并得到消费者认可,价格也不断攀升。因天然宝石级方钠石的宝石学特征和光致变色机理研究较薄弱,为鉴定提供理论依据并探究其变色机制,特选取具光致变色效应的天然白色方钠石分别进行UVA(365nm)和UVC(254 nm)紫外光致变色实验,并结合傅里叶变换红外光谱(FTIR)、紫外-可见光吸收光谱(UV-Vis)和电子顺磁共振波谱(EPR),探讨其光致变色机理。紫外光辐照实验显示,天然白色方钠石具有橙粉色-橙红色荧光,受UVA紫外光辐照5分钟变为紫红色,可维持1~2 min,使用白光（700~400 nm）照射可以快速褪至初始白色;受UVC紫外光辐照,紫色调浓度持续加深且产生持久稳定的光致变色;初始白色样品紫外荧光强度明显强于光致变色后紫红色样品。FTIR吸收光谱指示,5 250 cm-1处强吸收峰归属于H₂O的弯曲振动与伸缩振动的组合吸收,证实存在结晶水;4 698和4 555 cm-1两处弱吸收峰与金属阳离子(M)和O—H相互吸引而成的面外弯曲振动γ(M—OH)有关（M=Mg2+, Na+, K+, Al3+）;1 002 cm-1处强吸收峰与标准方钠石吸收特征相比,向高波数偏移约20 cm-1,指示硅氧四面体结构中AlⅣ含量减少,结合EPR波谱结果认为上述现象可能由Mn2+和Ti3+替换AlⅣ—O四面体结构所致,并分别形成以3 511 G(g=2.002)处为中心的多条超精细谱线及3 573 G(g=1.967)处单一谱线。UV-Vis和EPR谱指示,白色方钠石短波紫外产生持续光致变色产生的主要原因是,因S2-₂替代Cl-导致体系存在部分Cl缺失（空位V_Cl）来平衡电价,S2-₂受紫外线激发分解：S2-₂→S-₂+e-,e-进入导带而被V_Cl捕获形成色心,位于色心的电子转变为激发态而产生539 nm宽吸收带,伴有向紫外区的拖尾增强吸收,导致样品呈紫红色,EPR 3 480 G(g=2.02)处单一谱峰可作为判别依据。     

Conduction in ionic organic plastic crystals: The role of defects

This paper describes the relationship between the ionic conduction and the characteristics of defects in plastic crystalline phases of N,N-dimethylpyrrolidinium bis(trifluoromethanesulfonyl)amide (P₁₁TFSA). Positron annihilation lifetime spectroscopy (PALS) shows that the phase III to phase II transition involves the generation and expansion of vacancies, which is confirmed by measurement of volumetric expansion. The vacancies expand to match the cation size in phase II and this gives rise to an increase in the conductivity. The relationship between the vacancy volume and the conductivity obeys a Cohen–Turnbull free volume conduction model. The critical volume matches the volume of a cation–anion pair in phase III, which indicates a Schottky mechanism. The critical volume shows a greater value in phase II, which is probably indicative of a pipe diffusion mechanism.     

On the interaction of vacancies in a two-dimensional rare-gas crystal

We study the interaction between vacancies in a two-dimensional van der Waals crystal by molecular dynamics simulation. We find that the vacancy–vacancy interaction is attractive at short distances, but its binding energy is not enough to keep the pair bounded at the melting region where the vacancies are more likely to be created.     

嵌入原子法计算金属钚中点缺陷的能量

钚因放射性衰变而出现老化效应.钚中点缺陷的性质和行为是理解钚老化效应的一个基础和前提.运用分子动力学模拟技术,计算了金属钚中点缺陷和点缺陷团簇的形成能和结合能.其中钚-钚、钚-氦和氦-氦相互作用势分别采用嵌入原子多体势、Morse对势和Lennard-Jones对势.计算结果表明,单个自间隙原子易以〈100〉哑铃状形态存在;间隙氦原子在理想晶格的八面体间隙位置相对较为稳定;氦原子与空位的结合能较大,在钚的自辐照过程中两者易于结合并形成氦-空位团簇;氦-空位团簇的形成能随氦原子数的增加而增大,当氦与空位的数     

Interconnection of individual vacancy formation and pinning thermodynamic parameters in KCl

Tallon et al. have recently measured the individual thermodynamic parameters for cation vacancy and anion vacancy formation in KCl. Furthermore Tanibayashi and Tallon have just reported thermodynamic parameters of pinning in KCl. We show that the parameters of the above three processes are interconnected through well known properties of the bulk crystal.     

Relative energies of surface and defect states: ab initio calculations for the MgO (001) surface

We present the results of calculations of the energy levels of defects at the (001) surface of MgO relative to the top of the valence band and values of defect ionisation potentials and electron affinities. The calculations were made using an embedded cluster method in which a cluster of several tens of ions treated quantum mechanically is embedded in a finite array of polarisable and point ions modelling the crystalline potential and the classical polarisation of the host lattice. The calculated ionisation potential of the ideal surface, which fixes the position of the top of the valence band with respect to the vacuum level, is about 6.7 eV. This value is used as a reference for positioning the energy levels of three charge states of a surface anion vacancy, which are also calculated as ionisation energies with respect to the vacuum level. The surface and vacancy electron affinities are calculated using the same method. As a prototype low-coordinated surface site, we have considered a cube corner. Our calculations predict the splitting of the corner states from the top of the surface valence band by about 1.0 eV. Both unrelaxed and relaxed holes are strongly localised at the corner oxygen ion. The ionisation energies and electron affinities of the corner anion vacancy are calculated. The electrons in the F and F⁺ centres at the corner are shown to be significantly delocalised over surrounding Mg ions.     

FCC金属空位的MAEAM理论研究

应用涉及更远邻原子的改进分析型嵌入原子方法（MAEAM）计算了面心立方（fcc）金属（Ag,Al,Au,Cu,Ir,Ni,Pd,Pt,Rh）的空位性能。在MAEAM计算中,考虑了远邻原子相互作用和单空位迁移能,对两体势进行了坚挺处理,并采用新的截尾函数和加强光滑连接条件对两体势作了截尾处理。同时为了更好的符合面心立方晶体的结合能、弹性常数和平衡条件,调整了多体势的模型常数。未弛豫空位性能计算中考虑了两体势的截尾距离和电子密度分布函数的截尾距离之间近邻原子的作用以及双空位迁移途径周围的原子非对称分布。结果与其它方法计算结果基本一致,但更加接近实验值。对双空位迁移能的计算结果有利地说明了fcc金属双空位5种迁移途径的扩散机制。     

Solid–solid transformation route to nanocrystalline sodalite from Al-PILC at room temperature

The present study describes a solid–solid transformation of nanocrystalline sodalite from the solid gel mixture of Al₂O₃-pillared montmorillonite (Al-PILC) with sodium hydroxide at room temperature (25 °C) under an ambient atmosphere. Powder X-ray diffraction (XRD) analysis confirms that the X-ray crystalline sodalite products are crystallized after 12 days, whereas infrared absorption (IR) spectra reveal that diagnostic IR absorption peaks due to single four-membered ring of sodalite framework is observed even after 1 day. Scanning electron microscopy (SEM) shows that Al-PILC is transformed into discrete nano-sized sodalite particles (∼50 nm). Although the induction period, the time elapsing before nucleation, for the solid–solid transformation takes much longer (12 days), the nanocrystalline sodalite is successfully obtained at this extremely mild synthetic condition through solid–solid transformation.     

Study of ideal vacancies in ZnS and ZnO (Wurtzite)

The calculated states of ideal vacancies in ZnS and ZnO are calculated using a Green's function method in conjunction with the tight-binding approximation. Whereas the anion vacancy states are not found inside the band-gap, it is found that the Zn vacancy induces bound states in the gap in the case of ZnS or resonant states just below the top of the valence band in the case of ZnO. A brief discussion is made on the relation of the position of the levels to the ionicity of the material.     

Computer simulation of vacancy migration in a fcc tilt boundary

Vacancy jumps in a bicrystal model of Σ = 5 (36.9°) [001] tilt boundary in aluminum have been observed at temperatures between 700 and 800 K by means of molecular dynamics simulation. Preliminary results indicated considerable structure dependence and yielded an activation energy for vacancy migration of 0.38 eV. In contrast to a previous study of vacancy migration in a bcc tilt boundary, thermal activation of a boundary interstitial by Frenkel pair production was not observed.     

On the long-lived excited states and the spontaneous tunnel transitions in some positively charged color center systems in alkali halide crystals

A possible energy instability of some color center systems is pointed out, including an anion vacancy (α-center) in alkali halide crystals. When an optical electron passes from an F-aggregate center to an α-center, the system as a whole occupies a lower lying energy level. As an example the probability of the spontaneous radiative tunnel transition M + α → M⁺ + F in a KC1 crystal is calculated.     

Thermally stimulated depolarization measurements on NaF:02-, NaCI:S2-.and KC1:S2-

In NaCl:S^2-, KC1:S² and NaF:0^2-(i) optical absorption and emission spectra and (ii) electric conductivity measurements show that after suitable heat treatment the bivalent anion impurities are paired with anion vacancies. Conventional dielectric absorption measurements and sensitive measurements of thermally stimulated depolarizing (t. s. d.) currents (ionic thermocurrent) have failed to detect the presence of bivalent anion-anion vacancy dipoles in these crystals. We suggest that derealization or sharing of the electron of the bivalent impurity ion, possibly with the vacancy, considerably reduces the dipole moment.     

(29)Si hyperfine structure of the E(')(alpha) center in amorphous silicon dioxide

We report a study by electron paramagnetic resonance on the E'(alpha) point defect in amorphous silicon dioxide (a-SiO(2)). Our experiments were performed on gamma-ray irradiated oxygen-deficient materials and pointed out that the (29)Si hyperfine structure of the E'(alpha) consists of a pair of lines split by approximately 49 mT. On the basis of the experimental results, a microscopic model is proposed for the E'(alpha) center, consisting of a hole trapped in an oxygen vacancy with the unpaired electron sp(3) orbital pointing away from the vacancy in a back-projected configuration and interacting with an extra oxygen atom of the a-SiO(2) matrix.