钙钛矿型HoNiO3中电荷歧化的第一原理研究

应用第一原理的密度泛函方法,研究钙钛矿型过渡金属氧化物HoNiO_3的电子结构. HoNiO_3在正交结构（空间群为Pbnm）和单斜结构（空间群为P2_1/n）的电子密度图表明Ni在正交相中只存在Ni^３＋一种组态，而在单斜相中则存在Ni^(3-δ)+和Ni^(3+δ) +两种不同的组态. 电荷歧化特征值δ可由Ni3d电子态密度中非键t_2g部 分反映. 通过t_2g态密度在正交和单斜相的相对变化，可以算得δ 值为0.34±0.01. 关键词： HoNiO＿3 电荷歧化 电子结构 第一原理计算     

Ni_2P/介孔分子筛催化剂的原位漫反射红外光谱研究

以介孔分子筛MCM-41,MCM-48,SBA-15,SBA-16为载体,硝酸镍为镍源,磷酸氢二铵为磷源,通过浸渍法制备了含有磷化镍前体的介孔分子筛样品,然后在氢气气氛中进行程序升温还原,得到了磷化镍/介孔分子筛催化剂.采用原位漫反射红外光谱法,用CO作为探针分子,对样品的吸附特征进行了研究.结果表明,在介孔分子筛表面CO存在着较弱的物理吸附.在Ni2P/MCM-41催化剂样品表面有四种CO的吸附态:(1)在2055cm-1处形成的Ni(CO)4物种的吸附,(2)在2 091cm-1处的配位不饱和Niδ(0<δ<1)物种上的吸附,(3)在2 127 cm-1处的Ni+物种上的吸附,(4)在2 198～2 202 cm-1范围内的P物种上的吸附.在Ni2P/MCM-48,Ni2P/SBA-15,Ni2P/SBAZ-16催化剂样品表面有二种CO的吸附态:在2 051～2 055cm-1处的Ni(CO)4吸附和在2 093～2 096 cm-1处的配位不饱和Niδ+(0<δ<1)物种上的吸附.     

一维链状配合物[BrBzPy][Ni(dmit)2]的合成和红外光谱研究

合成了一种新的化合物[BrBzPy][Ni(dmit)2](1),并进行了红外光谱表征.晶体的结构结果表明它的空间点群为P21/c,a=0.627 5(1)nm,b=1.743 8(3)nm,c=2.283 9(3)nm,α=90°,β=9.187(1)nm,γ=90°,V=2.497(7)nm3,Z=4,Mr=700.57,Dc=1.863 g·cm-3.晶体中[Ni(dmit)2]-非常接近平面,共轭性相当显著,且成为一维链状结构.     

在D_2O溶液中DKDP晶体两相稳定区的研究

磷酸二氢钾(KH2PO4简称KDP)中的氢被其同位素氘取代后,所形成的磷酸二氘钾(KD2xH2-2xPO4简称 DKDP),具有两种晶相.一种属四方结构,空间群为　　,称为四方变体.另一种属单斜结构、空间群为　　;,称为单斜变体. 单斜晶体在空气中很不稳定,由于空气中的水气与晶体中氘的交换作用,透明晶体变模糊,进而变白松散,结果单斜结构转化成四方结构. 常用的DKDP晶体是四方变体.它具有优良的电光性能.在空气中物理、化学性能稳定,因此在激光调制、偏转和倍频等技术中得到广泛应用。 通常采用降温法培育四方DKDP晶体时,单斜相容易自发结晶和优先…     

三聚氰胺(C_3N_6H_6)的高压Raman与压致结构相变研究

本文在8 7GPa压力范围内研究了三聚氰胺(C3N6H6)的高压原位Raman光谱。通过内、外Raman活性模的压致效应,发现在1 5GPa和6 0GPa压力下该分子晶体发生了压致结构相变。用空间群相关原理确认在1 5GPa压力下它从单斜相转变为三斜相;在6 0GPa压力下又发生了另一次结构相变。然后在室温高压条件下对三聚氰胺进行了原位同步辐射能量散射x-ray衍射实验(EDXD),在14 7GPa压力范围内,观察到常压下为单斜晶系的三聚氰胺经历了两次压致结构相变。在1 3GPa下,三聚氰胺分子晶体从单斜相转变为三斜相;在8 2GPa又转变为正交相。本实验结果为利用三聚氰胺碳氮有机分子晶体高温高压合成超硬C3N4共价晶体的研究提供了重要信息。     

高压下CaF_2结构相变和光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方法,计算了在压力作用下CaF2的结构相变和光学性质。结果证实了CaF2的压致结构转变的顺序是从氟石结构(空间群Fm3m)转变到PbCl2型结构(空间群Pnma),然后继续转变为Ni2In型结构(空间群P63/mmc)。在Fm3m和Pnma两种结构中,电子带隙随着压力的增加而增加,而在P63/mmc结构中,带隙随着压力的增加开始下降。实验结果显示,直到210 GPa,CaF2没有发生由绝缘体到金属的转变。据此推测,CaF2的金属化压力高于300 GPa。还讨论了压力对CaF2光学性质的影响。     

Y_1Ba_2Cu_3O_(7-δ)的氧离子缺位数,氧空穴数变化与结构相变的关系

在空气、氮气、真空(10~(-3)乇)、氧气等气氛条件下,利用高温 X 射线动态跟踪法和 TG-DTA测定了 Y_1Ba_4Cu_3O_(7-δ)的结构和氧缺位量随温度的变化,注意到不同气氛对超导体中晶格氧和吸附氧的动态平衡的影响;测得氧缺位量δ与晶体结构转变之间的关系.根据文献[11]关于Cu-O 间电子转移的结论,计算出 Cu-O_2层中 O 的平均空穴数 n_h 与结构变化的对应关系.O≤δ≤0.25,0.25≥n_h≥0.125为正交超导相的稳定区,氧的空穴浓度为(1.44—0.72)x10~(21)/cm~30.25≤δ<0.5,0.125≥n_k>0为正交、四方相的转变过渡区;0.5≤δ≤1,n_h=0为四方非超导相的稳定区.因此,除了四方非超导结构区氧负离子取2价外,其它情况氧负离子也不总是取负2价.     

Y_1Ba_2Cu_3O_(7-δ)的氧离子缺位数,氧空穴数变化与结构相变的关系

在空气、氮气、真空(10^(-3)乇)、氧气等气氛条件下,利用高温 X 射线动态跟踪法和 TG-DTA测定了 Y_1Ba_4Cu_3O_(7-δ)的结构和氧缺位量随温度的变化,注意到不同气氛对超导体中晶格氧和吸附氧的动态平衡的影响;测得氧缺位量δ与晶体结构转变之间的关系.根据文献[11]关于Cu-O 间电子转移的结论,计算出 Cu-O_2层中 O 的平均空穴数 n_h 与结构变化的对应关系.O≤δ≤0.25,0.25≥n_h≥0.125为正交超导相的稳定区,氧的空穴浓度为(1.44—0.72)x10^(21)/cm^30.25≤δ<0.5,0.125≥n_k>0为正交、四方相的转变过渡区;0.5≤δ≤1,n_h=0为四方非超导相的稳定区.因此,除了四方非超导结构区氧负离子取2价外,其它情况氧负离子也不总是取负2价.     

Al-Ni-Co三元系中(Ni,Co)_3Al_4的晶体结构——一种由空位控制的新合金相

(Ni,Co)_3Al。是Al-Ni-Co三元系中的一种三元相,其均匀存在范围在室温为,55—58.5A/0Al,26—35A/0Ni和10-15.5A/0Co。这个三元相属立方晶系,空间群为O_k~(10)-Ia3d,每晶胞含112个原子,在室温的点阵常数为α=11.3962。 这个结构是由64个CsCI型基本结构单位堆垛而成的一种超结构。在这64个基本结构单位中,有16个体心位置是有序地空着的,在16(b)的等效位置上构成了16个八面体空位。基本结构单位的角位置16(a)和48(f)都由Al原子占据着,而心位置48(g)则由Ni原子和Co原子无规地占据着。由于空位的存在,原子位置从其原来的CsCl型结构单位位置有所偏离;测定的结果是,x_f=0.010,x_g=0.369。 从合金相的存在范围及原子在结构内的分布情况,这个合金相的理想化合式决定为(Ni,Co)_3Al_4,每单胞含16个化合式量。     

IrB和IrB_2力学性质的第一性原理计算

采用平面波赝势密度泛函理论对0—100 GPa静水压下P1-IrB(空间群Pnma)和P5-IrB2(空间群Pmmn)结构的平衡态晶格常数、弹性常数等性质进行了研究.研究结果表明,P1-IrB不可压缩性随着压强的增加而增强;P5-IrB2结构在0—100 GPa范围内弹性常数、体弹模量、剪切模量均呈现出有规律的变化,当所加压强为50 GPa时,杨氏模量和在b方向的晶格常数发生异常变化.对零压下P1-IrB和P5-IrB2的电子结构的研究发现,二者均没有一个明显的带隙,主要原因为Ir原子和B原子间的共价作用.从P1-IrB和P5-IrB2的能带结构和态密度图可以发现这两种结构均有金属性.     

Theoretical analysis and simulation of conjugate heights for dual-conjugate AO system in lidar

A multi-conjugate adaptive optics （MCAO） can offer a possibility of widening field of view （FOV） characterized by the isoplanatic angle, and the choose of conjugate height becomes a basic problem for MCAO, which influences the size of iosplanatic angle. Considering the application of lidar, the isoplanatic angle＇s expressions of two deformable mirrors （DMs） MCAO for uplink and downlink are deduced. The effects of conjugate heights for dual-conjugate AO are thoughtfully discussed, and the isoplanatic angles are further analyzed. The results show that the isopanatic angle varies with the conjugate height and reaches the maximum as the conjugate height is at the optimal altitude. Moreover, the optimal conjugate height changes with the propagation distance.     

Quick single-photon detector with many avalanche photo diodes working on the time division

Due to the limit of response speed of the present single-photon detector, the code rate is still too low to come into practical use for the present quantum key distribution (QKD) system.A new idea is put up to design a quick single-photon detector.This quick single-photon detector is composed of a multi-port optic-fiber splitter and many avalanche photo diodes (APDs).Au of the ports with APDs work on the time division and cooperate with a logic discriminating and deciding unit driven by the clock signal.The operation frequency lies on the number N of ports, and can reach N times of the conventional single-photon detector.The single-photon prompt detection can come true for high repetition-rate pulses.The applying of this detector will largely raise the code rate of the QKD, and boost the commercial use.     

Characterization of PolyA and PolyC mismatches by Raman spectroscopy

A.C mismatches are studied by Raman spectral characterization of PolyA, PolyC, and their equimolar complex in solution of 0.14 mol/L Na ,pH7.0.Experimental results show that A·C mismatches occur to be A/B (mainly A) conformers, and unlike Watson-Crick base pairing, this kind of mismatches is stabilized by only one hydrogen bond involving cytosine N4H2 and adenine N7.The formation of A·C complex makes the base stacking interactions much stronger, and conformation of the backbone more ordered, which leads to obvious Raman hypochromic effect with some shifts in corresponding bands.     

Improvement of four-wave mixing-based wavelength conversion efficiency in dispersion shifted fiber by 40-GHz clock pumping

40-GHz clock modulated signal as a pump to improve the efficiency of four-wave mixing (FWM)-based wavelength conversion in a 26.5-km dispersion shifted fiber (DSF) is investigated. The experimental results demonstrate that the conjugated FWM component has higher intensity with the clock pumping than that with the continuous-wave (CW) light pumping. The improvement of FWM-based wavelength conversion efficiency is negligible when the pump power is less than Brillouin threshold. But when the pump power is greater than Brillouin threshold, the improvement becomes significant and increases with the increment of pump power. The improvement can increase up to 9 dB if pump power reaches 17 dBm.     

Multi-pulse operation of a Kerr-lens mode-locked femtosecond laser

Our experimental results show that the presence of a proper amount of negative group velocity dispersion is essential to multi-pulse operation of a Kerr-lens mode-locked femtosecond laser. We demonstrate that the pulse separations and the number of pulses contained within a cavity round trip are strongly dependent on the initial perturbations. The results allow us to get a better understanding on the influences of the convoluted self-phase modulation and intra-cavity dispersions on the stable multi-pulse oscillation in a Kerr-lens mode-locked femtosecond laser.     

Propagation of Helmholtz-Gauss beams in weak turbulent atmosphere

Based on the Rytov approximation of light propagation in weak turbulent atmosphere,the closed-form expressions of field and average irradiance of each one of the four fundamental families of Helmholtz-Gauss (HzG)beams:cosine-Gauss beams,stationary Mathieu-Gauss beams,stationary parabolic-Gauss beams,and Bessel-Gauss beams,which are propagating in weak turbulent atmosphere,are obtained.The results show that the field and average irradiance can be written as the product of four factors:complex amplitude depending on the z-coordinate only,a Ganssian beam.a factor of complex phase perturbation induced by atmospheric turbulence,and a complex scaled version of the transverse shape of the non-diffracting beam.The effect of weak atmospheric turbulence on irradiance distribution of the HzG beam can be ignored.     

An effective method for reducing speckle noise in digital holography

An effective method for reducing the speckle noise in digital holography is proposed in this paper.Different from the methods based on classical filtering technique,it utilizes the multiple holograms which are generated by rotating the illuminating light continuously.The intensity images reconstructed by a series of holograms generated by rotating the illuminating light possess different speckle patterns.Hence by properly averaging the reconstructed intensity fields,the speckle noises can be reduced greatly.Experimental results show that the proposed method is simple and effective to reduce speckle noise in digital holography.     

Influence of purity of HfO2 on reflectance of ultraviolet multilayer

The impurities in two kinds of HfO2 materials and in their corresponding single layer thin films were determined through glow discharge mass spectrum technology and secondary ion mass spectrometry(SIMS) equipment respectively.It was found that ZrO2 was the main impurity in the two kinds of HfO2 either in the original HfO2 materials or in the electron beam deposited films.In addition,the difference of Zr content in the two kinds of HfO2 single laver films was much laxger than that of the other impurities such as Ti and Fe.which showed that it was just ZrO2 that made the difference between the optical performance of the film products including the two kinds of HfO2.With these two kinds of HfO2 and the same kind of SiO2.we deposited HfO2/SiO2 multilayer reflective coatings at the wavelength of 266 nm.Experimental results showed that the reflectances of these two mirrors were about 99.85% and 99.15% respectively,which agreed well with the designed results what were based on the optical constants obtained from the corresponding single layer thin films.     

Speech enhancement by array crosstalk resistant ANC and spectrum subtraction

Microphone array-based speech enhancement has great importance for speech communications and speech recognition. To reduce the aperture of the microphone array and to increase the effect of the speech enhancement will greatly broaden the application areas of the microphone array. An array crosstalk resistant adaptive noise cancellation method is therefore presented. And then an improved spectral subtraction algorithm is further cascaded to obtain better enhancement results. Theoretic analysis and experiments indicate that the proposed scheme needs only a very small microphone array while it simultaneously achieves a higher SNR improvement. Besides, the proposed scheme can be used in many noisy environments and is easy for real-time implementation.