ATaO_3（A=K,Na）电子结构和光学性质的第一性原理研究

采用第一性原理广义梯度近似（GGA）下的全电势线性缀加平面波（FP-LAPW）方法计算出立方相ATaO3（A=K,Na）的电子能带结构、态密度,发现了其光学性质.通过对两种材料的对比分析发现,KTaO3和NaTaO3价带顶均出现在0.15089eV处,KTaO3的导带底在2.02849eV处,NaTaO3的导带底在2.27339eV处,NaTaO3比KTaO3的导带底高,因而禁带宽度较大;NaTaO3中Ta5d电子和O2p电子之间的轨道杂化比KTaO3中的轨道杂化弱,Na的粒子性较K更强,因此,NaTaO3的光催化活性明显大于KTaO3.     

第一原理计算α-Al2O3电子态密度性质分析

利用第一性原理中的DFT理论计算了α-A l2O3晶体结构的能带结构和电子态密度,计算过程用软赝势表示原子芯区电子,结构优化后的晶格常数与实验值误差在很小的范围内.分析了A l和O的s和p轨道对分态密度的影响,依据晶体场理论分析了态密度成键轨道和反键轨道的归属.结果表明,禁带能隙约为8 eV,导带位于6.7~17.5 eV,对(110)晶面切片电子密度分析,发现氧原子周围强烈的电子定域分布.α-A l2O3电子的布居分析发现,在铝和氧之间存在明显电子转移.     

立方相WO_3电子结构及其(001)活性表面吸附性能

采用基于密度泛函理论的第一性原理方法探讨了WO3的电子结构和表面性能,进行了能带结构、态密度和有效电子质量的模拟计算,对WO3吸附12种原子后的吸附体系进行了理论分析。结果表明,WO3价带顶主要是由O的2p态电子构成,导带底主要是由W的5d态电子构成。当价带顶上的O-2p电子吸收能量后可跃迁至导带底的W的5d轨道上,同时在O-2p上产生空穴。其电子迁移率为1.35,表明其电子-空穴的分离率较高,光催化活性较强。探讨了WO3的(001)洁净表面对12种非金属原子的吸附情况,WO3吸附F原子后表面能最小。     

钙钛矿电子结构的密度泛函理论研究

应用密度泛函理论(DFT)计算方法,优化了K2Ti2O5的稳定几何构型,并计算了此钙钛矿体系的能带结构和态密度等基态物理性质.结果表明,K2Ti2O5属于间接绝缘体氧化物,其理论带隙宽度为2.6 eV.Ti原子处于氧原子的中心,其d轨道分裂为能量较高的eg和能量较低的t2g轨道,各轨道都靠近费米能级变为占据或半占据状态...     

团簇Co4P的成键及HOMO和LUMO轨道贡献

为深入了解Co-P非晶态合金的特性,在密度泛函理论中的B3LYP/Lanl2dz水平下对团簇Co_4P模型进行优化,最终得到6种优化构型.分别通过键长、键级以及态密度对团簇Co_4P的成键情况进行分析,得到以下结论:Co-P键对团簇Co_4P构型的稳定性提供了较大贡献; Co-P键的杂化方式包括p-d、 p-p和p-p-d 3种,其中Co-3d轨道与P-3p轨道形成了较强p-d杂化作用,进一步促进了Co-P键的稳定形成; Co-4s轨道、 P-3s轨道及P-3d轨道对团簇Co_4P的贡献极小.另外,通过对Co、 P原子的HOMO及LUMO轨道贡献率进行分析,发现Co原子是团簇Co_4P的潜在催化活性位点.     

Ni/BiFeO_3超晶格磁电效应的第一性原理计算

为了探究铁磁/铁电超晶格材料的磁电耦合效应,采用基于密度泛函理论的第一性原理计算方法,研究了Ni/BiFeO_3超晶格的电子结构和磁矩.结果表明,Ni/BiFeO_3超晶格界面处Ni-3d轨道与O-2p轨道发生了强烈的电子杂化作用,Ni和BiFeO_3界面主要通过以O原子为中间媒介的电荷转移进行相互影响.在外加电场作用下,由于铁电极化的存在,超晶格结构上下两个界面存在磁化差异,原子成键和电荷转移重新分布能够引起较强的磁电耦合效应. Ni/BiFeO_3超晶格界面磁电耦合系数约为3. 509×10-~(14)T·cm~2/V.     

闪锌矿结构ZnSe的光电性质和有效质量研究

为了研究红外透光闪锌矿ZnSe晶体光学性质和电学性质的内在机理。通过第一性原理的密度泛函理论,借助超软平面波赝势,计算了ZnSe晶体的能带结构和态密度,分析了反射光谱、吸收光谱和介电常数。基于有效质量的近似理论,计算了价带顶端附近电子的有效质量。研究结果表明:ZnSe晶体属于直接带隙半导体材料,反射峰的出现主要是因为Se原子的4p电子和Zn原子的3d态电子向导带跃迁,介电峰的分布与电子结构直接相关,介电峰主要是由于Zn的3d和Se的4p轨道价带向Zn的4s和Se的4s轨道导带的过渡。分析了价带顶端的电子有效质量,计算结果与文献资料基本一致,发现载流子的有效质量具有各向异性,k_a方向的电子和空穴的有效质量均较小。从而挖掘了ZnSe晶体的光电性质与有效质量的内在本质,这些分析结果对Ⅱ-Ⅵ族半导体光电子材料具有非常重要的参考价值。     

CO在Cu表面吸附过程中电荷转移的理论研究

应用密度泛函理论．对CO分子在Cu(100)表面的吸附过程进行了研究。计算了CO分子以垂直方式在3种不同吸附位置吸附时CO分子和Cu(100)表面原子的电荷分布。结果表明：与碳原子最近邻的铜原子表面上发生明显电荷转移．而其他表面原子及体相原子的电子结构没有变化。Mulliken集居数及局域态密度分析表明，吸附过程中CO分子与表面Cu原子相互作用主要是CO分子内杂化轨道和3d，4s，4p(Cu)的贡献。     

Coqn小团簇吸附活化原子氧的密度泛函研究

利用基于密度泛函理论（DFT）的Dmol3程序广义梯度近似PBE泛函,研究了Coqn（n=1~5;q=0, +, -）团簇和原子氧吸附在团簇上的几何结构、稳定性、电子性质和吸附反应行为。结果表明：Coqn团簇的几何结构保持不变,阳离子型团簇（Co+n）的平均结合能远大于中性型（Co0n）和阴离子型（Co-n）团簇的平均结合能,这是因为团簇失去一个电子后可以显著增强该团簇的稳定性;原子氧在Coqn团簇顶位、桥位、空位的吸附稳定性、Co—O键长、原子氧的电荷转移都呈现出规律性变化,说明原子氧被活化;Co-4 O B团簇的吸附能为-8.375 eV,轨道分析进一步表明其原子氧的2p轨道和钴的3d轨道杂化,相互作用为化学吸附。     

Co_(0.5)Zn_(0.5)Fe_2O_4/C复合物的制备及电磁性能研究

采用水热法制备出不同比的Co0.5Zn0.5Fe2O4/C复合物,通过X射线衍射分析仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)、振动样品磁强计(VSM)、网络分析仪对该复合物的形貌、电磁性能进行表征与分析。结果表明:Co0.5Zn0.5Fe2O4被碳包裹程度随碳相对含量的增加而增加;在频率为3~18 GHz范围内,Co0.5Zn0.5Fe2O4/C复合物的介电常数虚部和介电损耗随Co0.5Zn0.5Fe2O4的相对含量增加而增加;与Co0.5Zn0.5Fe2O4相比,Co0.5Zn0.5Fe2O4/C复合物的最大吸收峰有明显提高,且当0.5 g Co0.5Zn0.5Fe2O4与2 g葡萄糖混合时,制备的样品最大吸收峰在频率16 GHz左右可达到7 d B。     

Effect of Li content on the microstructure and properties of lead-free piezoelectric （K0.5Na0.5）1-xLixNbO3 ceramics prepared by SPS

Lead-free piezoelectric （K0.5sNa0.5）1-xLixNbO3 （x = 0at%-20at%） ceramics were synthesized by spark plasma sintering （SPS） at low temperature and the effects of LiNbO3 addition on its crystal structure and properties were also studied. When the Li content was less than 6at%, a single proveskite phase with the similar structure of （K0.5Na0.5）NbO3 was formed; and a secondary phase with K3Li2Nb5O15 structure was observed in the 6at% 〈 x 〈 20at% compositional range. Furthermore, LiNbO3 existed as the third phase when the Li content was higher than 8at%. The grain sizes increased from 200-500 nm to 5-8 μm when the K3Li2Nb5O15 and LiNbO3 like phases were formed. With increasing Li content, the relative density of the ceramics first decreased from 97% to 93% and then kept constant. The piezoelectric coefficient d33, dielectric constant, and planner electromechanical coupling factor exhibited a decreasing tendency with increasing Li content because of the decrease in density and the formation of the secondary phase such as K3Li2Nb5O15 and LiNbO3. The formation of dense microstructure with a single phase is necessary in improving the properties of the （K0.5Na0.5）1-xLixNbO3 ceramics.     

稀土Nd掺杂对Sr（Fe0.5Nb0.5）O3基介质陶瓷巨介电性能的影响

铁铌酸锶是一种重要的介质材料,具有复合钙钛矿结构,同其他介质材料相比,具有相对高的介电常数的优点,在高储能等领域有重要的应用潜力,是一种用途广泛的功能陶瓷材料．实验以Sr（Fe0.5Nb0.5）O3基陶瓷为研究对象,研究了稀土Nd掺杂对该系陶瓷巨介电性能的影响．结果表明：随着Nd抖掺杂量的增加,陶瓷样品的介电常数逐渐变大;随着温度的上升,陶瓷体系的介电常数也逐渐增大;Nd抖含量x≤0．10时,陶瓷样品有着良好的频率稳定性,x=0．10的陶瓷样品在100kHZ下有着良好的温度稳定性．     

Synthesis and Characteristic of a New Niobate:Ba_5NaCo_0.5Nb_9.5O_30

A new niobate crystal was synthesized for the first time in BaO-Na2O-Co2O3 -Nb2O5 system by solid state reaction and the flux method. The new compound was studied by X-ray diffraction, electron probe. N-ray microanalysis, chemical analysis and SEM. The result of the X-ray diffraction shows that Ba5 NaCo0.5 Nb9.5 OK) belongs to tetragonal tungsten bronze structure with space group P4bm( 100) and lattice parameters a = b = 12.4453(2) A, c = 3. 9770 (3) A and Z = 1. The structure of the compound is different from that of Ba4Na2Nb10O30     

Preparation,structure and dielectric properties of tungsten bronze ferroelectrics in SrO-Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Compounds Sr4Eu2Ti4Nb6O30 and Sr5EuTi3Nb7O30 with filled tetragonal tungsten bronze structure were prepared,and the dielectric characteristics and ferroelectric transition were investigated.Both ceramics displayed weak frequency dependence in room temperature dielectric constant,which decreased from 125 to 118 for Sr4Eu2Ti4Nb6O30,from 206 to 195 for Sr5EuTi3Nb7O30 in the frequency range of 10 kHz to 1 MHz.The present ceramics showed a diffuse ferroelectric phase transition.The frequency independent transition temperature (Tm) indicated the above compounds had no relaxor property.The diffuseness (γ) was 1.45 and 1.64 for Sr4Eu2Ti4Nb6O30 and Sr5EuTi3Nb7O30 respectively.The weak ferroelectric of the present materials are indicated from the P-E hysteresis loops,and a small 2Pr of 0.596 μC/cm2 and 0.068 μC/cm2 were observed for Sr4Eu2Ti4Nb6O30 and Sr5EuTi3Nb7O30 respectively.     

XRD STUDY ON PIEZOELECTRIC CERAMIC OF PZSN SYSTEM

The structure of piezoelectric ceramic in Pb[(Zn_(1/3)Nb_(2/3)(Sn_(1/2)Nb_2/3](Zr,Ti)O_3 system is studiedthrough XRD and TEM analysis.The effects of substitutionof Ba~(2 ), Sr~(2 ).for Pb~(2 )and small amount of dopants such asMnO_2 and Sb_2O_3 on the structure are investigated.The dif-ference between unpolarized and polarized XRD patternsand the structure of ferroelectric domains is emphaticallystudied.The result shows that the samples are of the tetrago-nal pertovskite-type structure.The dopants change the tetrago-nallty of samples and grain size but have no effect on thecrystal phase.The effects of polarizing on the structure canbe proved from the deformation of unit cell in microscopicstate and rotation of 90°ferroelectric domains in microscopicstate.     

Electronic Structure and Optical Properties of LiBiO_3 Doped with V,Nb,and Ta

The crystal structure, band structure, density of states, Mulliken charge, bond population and optical properties for LiBi_(1-x)M_xO_3(M=V, Nb, and Ta) were investigated using hybrid density functional theory. It was found that LiBiO_3 doped with V, Nb, and Ta presented distinctly stronger covalent interactions in M-O(M=V, Nb, and Ta) than Bi-O, thus resulting in mild distortion of the structure and facilitating the separation of photogenerated carriers. Furthermore, the hybridizations of Bi-6s, M-d(M=V, Nb, and Ta) and O-2p widened the valence and conduction bands, which promoted transmission of photogenerated carriers in the band edge and thus caused better photocatalytic performance.     

K0.5Bi0.5TiO3:ZnO无铅铁电复合陶瓷的退极化行为

为了抑制K_(0.5)Bi_(0.5)TiO_3的退极化现象,提高铁电性能,以K_2CO_3、TiO_2、Bi_2O_3及ZnO为原料,通过二步固相法合成无铅铁电复合陶瓷K_(0.5)Bi_(0.5)TiO_3:ZnO(KBT:ZnO).通过X射线衍射、扫描电子显微镜、铁电和介电测试分析了复合陶瓷的微观结构和介电行为.结果表明:KBT中引入20%(物质的量百分数)的ZnO后,复合陶瓷中生成了第三相Zn2TiO_4,同时,KBT的极化能力及其铁电行为得到改善.阻抗测试表明复合铁电陶瓷内部只存在一种导电机制,即电子电导.特别是ZnO的引入抑制了KBT由正常铁电体向弛豫铁电体的相转变,对KBT的应用和研究有着重要的作用.     

Electronic Structure and Optical Properties of LiBiO<Subscript>3</Subscript> Doped with V,Nb, and Ta

The crystal structure, band structure, density of states, Mulliken charge, bond population and optical properties for LiBi_1-xM_xO₃ (M=V, Nb, and Ta) were investigated using hybrid density functional theory. It was found that LiBiO₃ doped with V, Nb, and Ta presented distinctly stronger covalent interactions in M-O (M=V, Nb, and Ta) than Bi-O, thus resulting in mild distortion of the structure and facilitating the separation of photogenerated carriers. Furthermore, the hybridizations of Bi-6s, M-d (M=V, Nb, and Ta) and O-2p widened the valence and conduction bands, which promoted transmission of photogenerated carriers in the band edge and thus caused better photocatalytic performance.     

Struchre and Electrical Properties of (Na0.5Bi0.5)0.94Ba0.06TiO3 Ceramic with 0.5 wt% of MnO

The structure and electrical properties of(Na0.5Bi0.5)0.94Ba0.06TiO3 ceramic doped with 0.5 wt% of MnO were investigated in comparison with those of(Na0.5Bi0.5)0.94Ba0.06TiO3 ceramic.It was ascertained that the MnO addition did not cause remarkable change in crystal structure and microstructure.The MnO addition mainly displayed a hard effect on the electrical properties,an increase of coercive field(Ec)and mechanical quality factor(Qm)together with a decrease of dielectric constant(?r)and piezoelectric constant(d33).An enhancement of electromechanical coupling factor(kp)with the MnO addition was obtained too.An essential relation between the piezoelectric properties and ferroelectric nature of the ceramics was detected.It was found that the piezoelectric properties of the ceramics highly depended on the corporative contribution of remanent polarization(Pr)and coercive field.     

Synthesis and Dielectric Properties of New Niobate Ba_5BiTi_3Nb_7O_(30)

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