高压下TiAl3结构及热动力学性质的第一性原理研究

采用平面波赝势密度泛函理论研究了钛铝系金属间化合物TiAl₃的结构性质, 计算值与实验值及其他理论值相符合. 通过准谐德拜模型研究了TiAl₃的热动力学性质, 计算得到了相对体积(V/V₀)与压强和温度的关系, 以及不同温度和压强下的热膨胀系数和热容. 与TiAl的计算结果进行对比, 发现随着温度的升高, TiAl的热膨胀系数增大的速度高于TiAl₃, 且随着压强的增大温度效应减弱; TiAl₃的热容值近似为TiAl的热容值的2倍. 关键词： 结构性质 热动力学性质 第一性原理 高压     

CeO2热力学性质的第一原理研究

使用第一性原理方法结合准谐德拜模型研究压力0~30 GPa,温度0~2 000 K,二氧化铈立方结构的热力学性质,包括常压下平衡体积V、体弹模量B₀、热容c_p和熵S随温度的变化以及不同压强下热容c_p、熵S、德拜温度Θ,体膨胀系数α与温度的关系.常压下计算的热容c_p和熵S随温度的变化与实验数据符合很好.     

高压下ErNi2B2C弹性性质、电子结构和热力学性质的第一性原理研究

采用密度泛函理论中的赝势平面波方法研究了高压下超导材料 ErNi₂B₂C 的弹性性质、电子结构和热力学性质.分析表明, 弹性常数、体弹模量、剪切模量、杨氏模量和弹性各向异性因子的外压力效应明显. 电子态密度(DOS)的计算结果显示, 在费米能级(E_F)处的 DOS 峰随外界压强的增大显著降低, 由于 ErNi₂B₂C 相对较高的超导温度(T_c)起因于E_F处的 DOS 峰, 因此推测压强增大可能会降低 ErNi₂B₂C 的 T_c.类似的现象在超导材料 MgB₂和 SrAlSi 中已被发现.此外, 基于准谐德拜模型, 对 ErNi₂B₂C 在高温高压下的热力学性质的研究表明, 在一定范围内, 温度和压强将对其热膨胀系数和热容产生明显的影响. 关键词： 高压 弹性性质 电子结构 热力学性质     

高压下TiC的弹性、电子结构及热力学性质的第一性原理计算

利用基于密度泛函理论的第一性原理平面波赝势方法 并结合准谐徳拜模型研究了NaCl结构的TiC在高压下的弹性性质、电子结构和热力学性质. 计算所得零温零压下的晶格常数、体弹模量及弹性常数与实验值符合得很好. 零温下弹性常数和弹性模量随压强增大而增大. 通过态密度和电荷密度的分析, Ti-C键随压强增大而增强. 运用准谐德拜模型, 成功计算了TiC在高温高压下的体弹模量、熵、热膨胀系数、徳拜温度、 Grüneisen参数和比热容. 结果表明压强对体弹模量、热膨胀系数和徳拜温度的影响大于温度对其的影响. 热容随着压强升高而减小, 在高温高压下, 热容接近Dulong-Petit极限.     

常压下固态KNO2热力学性质的密度泛函理论研究

采用密度泛函理论结合准谐德拜模型研究常压下300~725 K间KNO₂立方结构的热力学性质,重点分析常压下定压热容、定容热容、熵、德拜温度、体膨胀系数、平衡体积和体弹模量随温度的变化.结果显示,常压下计算的定压热容随温度的变化与实验数据符合较好,而计算的熵与实验数据相差较大.计算得到KNO₂的平均体膨胀系数约为1.837 8×10^-5K^-1,常温下(300 K)KNO₂的德拜温度约为667.13K.     

ZrH_2结构与热力学性质

基于密度泛函理论,采用全势线性缀加平面波加局域轨道方法和广义梯度近似研究了ZrH2的结构与弹性性质。结果表明:在基态条件下,ZrH2的晶格常数计算值与实验值及其它理论值相当吻合。在考虑声子作用的前提下,采用准谐德拜模型成功获得了不同条件下(0~50 GPa,0~1 300 K)ZrH2的热容、热膨胀系数和德拜温度等热力学性质。结果表明:定压热容预测值随温度升高而增大,并逐渐接近佩蒂特-杜隆极限;随压强增加,德拜温度呈增加趋势;随温度增加,德拜温度呈减小趋势;在压强一定的条件下,热膨胀系数随温度的升高而增大,且在高温高压条件下,热膨胀系数的增加趋势变缓。     

ZrV2结构、弹性和热力学性质的第一性原理计算

采用基于密度泛函理论的第一性原理平面波赝势方法研究ZrV₂的晶体结构和弹性,利用准谐Debye模型计算在不同温度(T=0~1200 K)和不同压强(P=0~20 GPa)下ZrV₂的热力学性质,包括弹性模量与压强,热熔与温度,以及热膨胀系数与温度和压力的关系.结果表明:计算的ZrV₂晶格常数与实验值符合较好,晶体材料的弹性常数随着压力增加而增加;在一定温度下,相对体积、热熔随着压强的增加而减小,德拜温度、弹性模量随着压强的增加而增加,且高压下温度对ZrV₂热膨胀系数的影响小于压强的影响.     

温度和压强对金属化合物Co_2Zr和Co_2Ti的结构和热力学性质影响的研究

基于平面波赝势密度泛函理论(DFT)和广义梯度近似(GGA)的第一性原理计算了高温高压下金属化合物Co_2Zr和Co_2Ti的结构和热力学性质.Co_2Zr和Co_2Ti均为立方晶体,且结构类型为Cu2Mg结构.通过计算得出的晶格参数跟实验值符合较好.用准谐德拜模型计算了Co_2Zr和Co_2Ti的热力学性质.在0~100 GPa的压强和0~1500 K的温度作用下,两种物质的德拜温度Θ,热容CV,热膨胀系数α随压强和温度的变化而变化.随着压强的增大,德拜温度单调的增加;相同压强下,Co_2Ti的德拜温度始终大于Co_2Zr.热容CV和热膨胀系数α均随温度的增加而增加,增大压强时反而减小,说明减小温度和增大压强对CV以及α有相同的影响.     

高压下Ni_3Al热力学性质的第一性原理研究北大核心CSCD

运用第一性原理方法结合准谐Debye-Grüneisen模型研究了高压下Ni3Al的热力学性质,拟合了Ni3Al的状态方程,计算了不同压强下Ni3Al的弹性模量及吉布斯自由能等热力学性质随温度的变化关系.计算结果表明:采用七阶Birch-Murnaghan方程拟合的晶格常数与实验测量结果吻合较好;零压下弹性模量、吉布斯自由能、焓、熵、热容和体膨胀系数随温度的变化与实验值符合较好;在特定压强下,Ni3Al的弹性模量和吉布斯自由能随温度升高而减小,焓、熵随温度升高而增加;预测的德拜温度约为500K,与实验值符合较好.     

高压下硫化钙的弹性和热力学性质的第一性原理计算

利用基于密度泛函理论的第一性原理平面波赝势方法结合准谐德拜模型研究NaCl结构的CaS在高压下的弹性和热力学性质.计算得到的零温零压下的晶格常数、体弹模量与实验值符合得很好.弹性常数和弹性模量随着压强的增大而增大.压强对体弹模量和热膨胀系数的影响大于温度的影响.热容随压强的升高而降低,在高温下热容接近于Dulong-Petit极限.通过求解Gibbs自由能计算得到B1结构和B2结构CaS的相变压为36.61 GPa.     

Fine structure and isotope shift of the 3s4d 3 D-3s3p 3 P, 3s5d 3 D-3s3p 3 P and 3p 2 3 P-3s3p 3 P Transitions of MgI

Summary We report the measurements of the³ D(3s4d)-³ P(3s3p)³ D(3s5d)-³ P(3s3p), and³ P(3p ²)-³ P(3s3p) transition frequency of MgI, the fine-structure separation and isotope shift between²⁴Mg and²⁶Mg. The measurements have been performed in a metastable atomic beam; a good agreement is found for data already existing in the literature. The accuracy of the measurements reported in this paper is mainly limited by the Doppler broadening of theI ₂ transitions used as a reference and by the precision in the knowledge of the related wavelengths.     

The gas phase infrared band contours of s-triazine and s-triazine-d3: The fundamentals of C3N3H3 and C3N3D3 and some overtone and combination bands of C3N3H3

The systematic application of band contour techniques to account for most of the observed features of the ir spectra of s-triazine and s-triazine-d₃ have been made as well as a critique as to the limitations of such methods. The experimental and computer methods used to study the gas phase infrared band contours of s-triazine and s-triazine-d₃ are out-lined. Contours of the five E′ fundamentals of s-triazine have been recorded under moderate resolution and analyzed to give the Coriolis constants $\text{ζ}{}_{\mathrm{i}}{}^{\mathrm{z}}$, i = 6–10. The effects of l-resonance are very apparent for ν₈ and ν₉, in the form of holes in the Q branches of these bands. Under the highest resolution available, ν₆ and ν₁₀ also show l-resonance effects. Values of the l-doubling constants $\text{q}{}_{\mathrm{i}}{}^{\mathrm{(+)}}$ were obtained for these four fundamentals. One of the parallel A₂″ fundamentals of C₃H₃N₃ (ν₁₂) has also been studied. It lies close to ν₁₀(E′) and an A × E type of second-order Coriolis resonance may be the cause of the intensity enhancement observed in the inner wings of the ν₁₂ and ν₁₀ bands. Hot bands of the type (ν_i + nν₁₄ ? nν₁₄) have been observed in the contours of ν₈, ν₁₀, and ν₁₂. This is felt to be responsible for the large difference between our observed zeta sum (?1.30) and the theoretical sum (?1.00).The gas phase infrared band contours of the five E′ and 2A₂″ fundamentals of C₃N₃D₃ have also been recorded under moderate resolution. From P-R separations and by computer simulation of the contours, values of the Coriolis constants $\text{ζ}{}_{\mathrm{i}}{}^{\mathrm{z}}$ have been obtained for the E′ modes. The effects of l-resonance have been observed for ν₈(E′) and ν₁₀(E′) and values of the l-doubling constants $\text{q}{}_{\mathrm{i}}{}^{\mathrm{(+)}}$ have been estimated. An extensive series of hot bands of the type (ν₁₂ + nν₁₄ ? nν₁₄) has been observed in the contour of the ν₁₂ (A₂″) fundamental. The mass effect on the Coriolis constants has been discussed.Infrared band contours of the overtone 2ν₇ and seven degenerate E′ combination bands of C₃N₃H₃ have been recorded under moderate resolution. Analysis of these contours using the P-R separation method and computer simulation of the contours has given values of $\text{ζ}{}_{\mathrm{<mtext>eff</mtext>}}{}^{\mathrm{z}}$ for these bands. Fermi resonance between 2ν₇ and ν₆ has been analyzed. The importance of considering both the observed contour as well as the observed frequency when assigning higher tone bands is illustrated.     

Dielectric investigations of solid solutions SrTiO3-KTaO3 and SrTiO3-KNbO3

The temperature dependences of the dielectric constant and dielectric hysteresis loops in ceramic samples of (1 ? x)SrTiO_3?x KNbO₃ and (1 ? x)SrTiO_3?x KTaO₃ (0 ≤ x ≤ 0.3) solid solutions prepared using different heat treatments have been investigated. Phase diagrams of the studied solid solutions have been constructed in the T-x coordinates. It has been shown that, after quenching of samples (spontaneous cooling at room temperature after long-term heating at the sintering temperature of the ceramic samples), the temperature of the induced phase transition increases because of the weakening of random electric fields associated with nonisovalent impurities due to their “frozen” nonequilibrium redistribution. For small concentrations x, strong dielectric relaxation is observed in the temperature range of 150–250 K. A model of relaxing centers, which is based on the local charge compensation of heterovalent impurities, has been proposed.     

Infrared spectra of matrix isolated BH3NH3, BD3ND3, and BH3ND3

The infrared spectra of ammonia-borane, BH₃NH₃, and two of its deuterated isotropic species, BD₃ND₃ and BH₃ND₃, isolated in argon matrix at liquid hydrogen temperature have been measured. Well resolved bands for these three isotopic species have been observed for all the fundamentals. A complete frequency assignment based on C₃v molecular symmetry has been made. A set of force constants have been calculated from the data for the two isotopes BH₃NH₃ and BD₃ND₃ using a valence force field. The agreement between experiment and frequencies calculated from these force constants for the mixed isotopic species, BH₃ND₃, substantiates the present assignment.     

Modulated magnetic structures of ErPb3, HoPb3, ErTl3 and HoTl3

Neutron diffraction experiments have been carried out on the magnetically ordered phases of ErPb₃, HoPb₃, ErTl₃ and HoTl₃. The magnetic moments were found to be sinusoidally modulated with a propagation vector of (0, 0.2, 0.5) for the Pb-compounds and (0.38, 0.38, 0.16) for the Tl-compounds.Work supported by the Bundesministerium für Forschung und Technologie     

Ba3La(BO3)3基质中Tb3+的光致发光

以高温固相法合成了Ba3La(BO3)3∶Tb3 发光材料。在254nm紫外光激发下,研究了Ba3La(BO3)3∶Tb3 的激发光谱、发射光谱、发光强度与Tb3 浓度的关系。确定了Ba3La(BO3)3基质中Tb3 的自身浓度猝灭机理;探讨了助熔剂LiCO、敏化剂Ce3 、Bi3 的加入对荧光粉的发光强度的影响。     

Far Infrared Spectra of Ammonia-Boron Trifluoride: NH3BF3 and ND3BF3

Abstract

Spectra of polycrystalline samples of NH₃BF₃ and ND₃BF₃ at 300 K and 98 K have been recorded in the frequency range 20-400 cm^?1. Isotopic frequency ratios are used to interpret the observed features in terms of the known molecular and crystal structures.     

Improvement of Photoluminescence of Perovskite CH_3NH_3Pb I_3 by Adding Additional CH_3NH_3I during Grinding

The organic-inorganic hybrid perovskite CH_3NH_3PbI_3 has been a good candidate for many optoelectronic applications such as light-emitting diodes due to its unique properties.Optimizing the optical properties of the CH_3NH_3PbI_3 material to improve the device performance is a hot topic.Herein,a new strategy is proposed to enhance the light emission of CH_3NH_3PbI_3 phosphor effectively.By adding the reactant CH_3NH_3I powder in an appropriate proportion and simply grinding,the emission intensity of CH_3NH_3PbI_3 is greatly improved.The advantages of the proposed method are swiftness,simplicity and reproducibility,and no requirement for a complex organic ligand.The mechanism of this phenomenon is revealed by x-ray diffraction,scanning electron microscopy,energy dispersive spectroscopy,photoluminescence,and temperature-dependent photoluminescence.This study offers a unique insight for optimizing the optical properties of halide perovskite materials.