NMR Analysis of a Complex Spin System from a Siruo-Chamigrene

The compound 2,10-dibromo-3-chloro-8-hydroxy-β-chamigrene was analysed in detail by NMR Spectroscopy. the complete assignment of the signals in the ¹H and ¹³C NMR spectra and the determination of the relative configurations were achieved by 2D NMR techniques, AM1 data and ¹H spectrum simulation. Comparisons of the results with related spiro chamigrene systems are also presented.     

In-situ X-ray diffraction study on β-CrOOH at high pressure and high-temperature

ABSTRACT

High pressure hydrous phases with distorted rutile-type structure have attracted much interest as potential water reservoirs in the Earth’s mantle. An in-situ X-ray diffraction study of β-CrOOH was performed at high pressures of up to 6.2?GPa and high-temperatures of up to 700?K in order to clarify the temperature effect on compression behaviors of β-CrOOH. The P-V-T data fitted to a Birch–Murnaghan equation of state yielded the following results: isothermal bulk modulus K_T0?=?191(4)?GPa, temperature derivative (?K_T/?T)_P?=??0.04(2)?GPa?K^?1, and volumetric thermal expansion coefficient α?=?3.3(2)?×?10^?5?K^?1. In this study, at 300?K, the a-axis became less compressible at pressures above 1–2?GPa. We found that the pressure where the slopes of a/b and a/c ratios turned positive increased with temperature. This is the first experimental study indicating the temperature dependence of the change in the axial compressibility in distorted rutile-type M³⁺OOH.     

First-principles calculations of structural and thermodynamic properties of β-PbO

We employed ab-initio calculations to investigate the structural and thermodynamic properties of Massicot or orthorhombic phase of PbO named β-PbO using the projector augmented-wave(PAW) method within the generalized gradient approximation(GGA). The temperature and pressure dependence of bulk modulus, heat capacity at constant pressure and constant volume, entropy, thermal expansion coefficient and Grüneisen parameter were discussed. Accuracy of two different models, the Debye and Debye-Grüneisen which are based on the quasi-harmonic approximation(QHA) for producing thermodynamic properties of material were compared. According to calculation results, these two models can be used to designate thermodynamic properties for β-PbO with sensible accuracy over a wide range of temperatures and pressures, and our work on the properties of this structure will be useful for more deeply understanding various properties of this structure.     

Simulation of near-infrared photodiode detectors based on β-FeSi_2/4H-SiC heterojunctions

In this paper,we propose a near-infrared p-type β-FeSi2/n-type 4H-SiC heterojunction photodetector with semiconducting silicide(β-FeSi2) as the active region for the first time.The optoelectronic characteristics of the photodetector are simulated using a commercial simulator at room temperature.The results show that the photodetector has a good rectifying character and a good response to near-infrared light.Interface states should be minimized to obtain a lower reverse leakage current.The response spectrum of the β-FeSi2/4H-SiC detector,which consists of a p-type β-FeSi2 absorption layer with a doping concentration of 1×1015cm-3 and a thickness of 2.5 μm,has a peak of 755 mA/W at 1.42 μm.The illumination of the SiC side obtains a higher responsivity than that of the β-FeSi2 side.The results illustrate that the β-FeSi2/4H-SiC heterojunction can be used as a near-infrared photodetector compatible with near-infrared optically-activated SiC-based power switching devices.     

Resonant energy transfer from nanocrystal Si to β-FeSi2 in hybrid Si/β-FeSi2 film

The photoluminescence （PL） characteristics of hybrid β-FeSi2/Si and pure β-FeSi2 films fabricated by pulsed laser deposition at 20 K are investigated. The intensity of the 1.54-μm PL from the former is enhanced, but the enhancement vanishes when the excitation wavelength is larger than the widened band gap of Si nanocrystal. Time-resolved PL decay measurements reveal that the lifetime of the photo-excited carriers in the hybrid β-FeSi2/Si film is longer than that in the pure β-FeSi2 film, providing evidence that the PL enhancement results from the resonant charge transfer from nanocrystalline Si to β-FeSi2.     

β-胡萝卜素分子的黄琨因子的温度特性

β-胡萝卜素具有光采集、光防护功能, 又是重要的光电材料, 它在外场下的分子结构和性能变化既有理论意义也有应用价值。测量了β-胡萝卜素在环己醇中68～26 ℃温度范围内的紫外-可见吸收、拉曼光谱。实验结果表明随着温度的降低, 黄琨因子和碳碳键每个振动模的电子-声子耦合常数减小, 紫外-可见吸收光谱红移, 碳碳键拉曼散射截面增加。用线性链状多烯分子的“相干弱阻尼电子-晶格振动模型”、“有效共轭长度模型”等理论给予了解释。随着温度的降低,β-胡萝卜素分子的热无序减小,分子结构有序性增加,π电子离域扩展,有效共轭长度增加,导致紫外-可见吸收光谱红移和强的拉曼活性。相干弱阻尼电子-晶格振动增强,使碳碳键拉曼散射截面增加。引用带有量纲的电子-声子相互作用常数,既可以与黄昆因子建立关系式,计算出碳碳键每个振动模的数值,也可以表征分子的有效共轭长度,π电子离域程度及拉曼散射截面的大小等。     

α,α'-二氧代烯酮环二硫代缩醛的NMR研究

报道了7种新的α,α'-二氧代烯酮环二硫代缩醛化合物的NMR谱.应用¹H、¹³C NMR谱等确定了这7种新化合物的分子结构,并对全部谱峰进行了归属,初步探讨了分子结构对化学位移的影响.     

β型烧绿石氧化物超导体AOs2O6 (A=K, Rb) 的 声子软化与超导电性

运用基于密度泛函理论的第一性原理计算方法, 研究两种β 型烧绿石氧化物超导体AOs₂O₆(A=K, Rb) 的结构稳定性, 声子软化以及与超导电性的关系. 通过计算发现, AOs₂O₆中碱金属原子A(=K, Rb) 沿〈111〉 晶向具有不稳定性, 且以K原子的不稳定性更为突出. 同时, 计算得到的KOs₂O₆在布里渊区中心的声子频率普遍比RbOs₂O₆的低, 使得KOs₂O₆的电声子耦合常数比RbOs₂O₆的大. 本文计算结果表明, 较小的碱金属原子K位于较大的氧笼子中, 活动性较强, 导致声子的软化, 是引起KOs₂O₆具有较强的电声子耦合及较高的超导转变温度的根本原因. 这些结果对解释两种β 型烧绿石氧化物超导体AOs₂O₆(A=K, Rb) 的超导电性具有重要意义.     

β-Expectation tolerance regions for a generalized multivariate model with normal error variables

In this paper a procedure of construction of β-expectation tolerance regions in the framework of the structural method of inference has been developed. The procedure has been applied to the generalized multivariate model and the β-expectation tolerance region for this case has been constructed assuming the normal distribution for the error variables of the model.     

B,P掺杂β-Si3N4的电子结构和光学性质研究

运用第一性原理方法, 计算了B, P两种元素单掺杂和共掺杂的β -Si₃N₄材料的电子结构和光学性质. 结果表明: B掺杂体系的稳定性更高, 而P掺杂体系的离子性更强; 单掺和共掺杂均窄化带隙, 且共掺在禁带中引入深能级, 使局域态增强; 单掺杂体系介电函数虚部、吸收谱和能量损失谱各峰均发生红移、幅值减小, 而共掺后介电函数虚部主峰出现蓝移、能量损失峰展宽、高能区电子跃迁大大增强, 且控制共掺杂的B, P比例可获得较低的带电缺陷浓度.