掺杂元素对Mg2NiH4稳定性影响的第一性原理研究

本文采用基于密度泛函理论(DFT)的第一原理赝势平面波(PW-PP)方法,计算了低温相Mg2NiH4和(Mg2Ni,X)H4(X=Ag, Al, Ti或Zr)的生成热及电子结构,分析了掺杂元素对Mg2Ni氢化物稳定性的影响. 结果表明,掺杂导致了合金氢化物生成热的绝对值降低,合金氢化物的稳定性下降,且发现掺杂元素电负性越大,氢化物越不稳定. 从电子态密度图和Mulliken布居数分析知道,掺杂后合金氢化物释氢能力增强的主要原因在于Ni-H之间的成键减弱,以及掺杂元素诱导费米能级EF处电子数浓度N(EF)的增加.     

掺杂元素对Mg2NiH4稳定性影响的第一性原理研究

本文采用基于密度泛函理论(DFT)的第一原理赝势平面波(PW-PP)方法,计算了低温相Mg2NiH4和(Mg2Ni,X)H4(X=Ag, Al, Ti或Zr)的生成热及电子结构,分析了掺杂元素对Mg2Ni氢化物稳定性的影响. 结果表明,掺杂导致了合金氢化物生成热的绝对值降低,合金氢化物的稳定性下降,且发现掺杂元素电负性越大,氢化物越不稳定. 从电子态密度图和Mulliken布居数分析知道,掺杂后合金氢化物释氢能力增强的主要原因在于Ni-H之间的成键减弱,以及掺杂元素诱导费米能级EF处电子数浓度N(EF)的增加.     

NiH2分子的结构及其势能函数

应用群论及原子分子反应静力学方法推导了NiH2分子基态的电子态及其离解极限,在MP2/6-311G水平上,优化出NiH2(3Δg)分子稳定构型为D∞h,其平衡核间距Re=0.157 3 nm、∠HNiH=180.00°,同时计算出振动频率:对称伸缩振动频率ν1=2 000 cm-1,弯曲振动频率ν2=721 cm-1和反对称伸缩振动频率ν3=1 875 cm-1.在此基础上,使用多体项展式理论方法,导出了基态NiH2分子的全空间解析势能函数,该势能函数准确地再现了NiH2(D∞h)平衡结构.     

Hydrogenation-induced insulating state in the intermetallic compound LaMg2Ni

Hydrogenation-induced metal-semiconductor transitions usually occur in simple systems based on rare earths and/or magnesium, accompanied by major reconstructions of the metal host (atom shifts >2 A). We report on the first such transition in a quaternary system based on a transition element. Metallic LaMg2Ni absorbs hydrogen near ambient conditions, forming the nonmetallic hydride LaMg2NiH7 which has a nearly unchanged metal host structure (atom shifts <0.7 A). The transition is induced by a charge transfer of conduction electrons into tetrahedral [NiH4]4- complexes having closed-shell electron configurations.     

Resolved fluorescence spectra of NiH. Electronic structure,electronic energy transfer,and the Zeeman effect in low-lying states

Fourier transform spectra of collisionally induced fluorescence following isotopically selective laser excitation of NiH at ～550?nm have located an excited Ω?=?1/2 state of NiH lying 17900?cm^?1 above the electronic ground state. This is identified as v?=?0 of a ²Π_1/2 state originating from an Ni⁺ 3d⁸4s^{1 2}F configuration. Emission from this Ω′?=?1/2 state occurs predominantly to v″?=?0 and 1 of the ²Σ⁺ and W₂ ²Π_1/2 ligand field states, locating elusive f parity levels of W₂ ²Π_1/2 up to 5600?cm^?1 above the first rotational level of the electronic ground state, X ₁ ²Δ_5/2. Collisionally induced fluorescence following laser excitation at lower energies has also been recorded in the presence of a magnetic field (0.7–1?T), at Doppler limited resolution. Effective Landé factors g _J for rotational levels of the v?=?0 and 1 levels of the low-lying Ω″?=?5/2 and 3/2 components of the ²Δ and ²Π states of NiH have been derived from partially resolved Zeeman patterns. About 1600 transitions recorded in field-free conditions have been reduced to term energies relative to the lowest level of the ground state. They confirm strong spin-orbit mixing between the low-lying ligand-field states.     

Dual-functional diffraction grating based on selective metal deposition of photochromic diarylethene

Dual-functional diffraction gratings, which show different diffractions in transmission and reflection, are proposed as an essential optical element. We utilize a flattening effect of photochromic diarylethene (DAE) in the low glass transition temperature state and selective metal deposition to prepare the gratings. The uncolored lines of the colored DAE layer on a grating substrate with grooves were formed by red-laser scanning, and Mg evaporation onto the substrate without a shadow mask enabled Mg-line formation at right angles to the grooves. After being stored at 27 °C for 500 min, the sample showed two-dimensional diffraction in reflection but one-dimensional diffraction in transmission, meaning that a dual-functional grating was achieved. This result shows great potential as a key element for various future optical devices and systems.     

Mg掺杂ZnO纳米晶的低温共沉淀法制备及光学性质

采用共沉淀(co-precipitation)法制备了Mg掺杂ZnO纳米晶,分别用X射线衍射(XRD)、傅立叶变换红外光谱(FTIR)、紫外可见吸收(UV-Vis)光谱、光致发光(PL)光谱、透射电镜(TEM)、电子顺磁共振(EPR)等分析手段对样品进行了表征。探究了Mg离子在ZnO纳米晶中的存在状态,ZnO纳米晶颗粒尺寸和发射光谱随Mg掺杂浓度的变化,并对其发光机理进行了分析。结果表明:Mg离子在ZnO晶格中以部分晶格位,部分间隙位的方式存在,没有形成MgO表面壳层结构;随Mg掺杂浓度的增大,ZnO纳米晶的颗粒尺寸变小,发射光的光强增大。发射光的最佳激发波长为342nm,中心波长为500nm,荧光量子产率为22.8%。实验分析表明:Mg离子的掺杂在ZnO纳米晶中引入了锌空位(VZn),间隙位的镁离子(IMg),提供了新的复合中心,从而增强了ZnO纳米晶的光致发光。     

First-principles prediction of a ground state crystal structure of magnesium borohydride

Mg(BH(4))(2) contains a large amount of hydrogen by weight and by volume, but its promise as a candidate for hydrogen storage is dependent on the currently unknown thermodynamics of H2 release. Using first-principles density-functional theory calculations and a newly developed prototype electrostatic ground state search strategy, we predict a new T=0 K ground state of Mg(BH(4))(2) with I4[over ]m2 symmetry, which is 5 kJ/mol lower in energy than the recently proposed P6(1) structure. The calculated thermodynamics of H(2) release are within the range required for reversible storage.     

Mg3N2和Mg3B2N4触媒的研究

 本文由实验确定了常压下合成的Mg₃B₂N₄触媒和Mg₃N₂-BN体系在高温高压下都转变成相同的高压相Mg₃B₂N₄。本文还讨论了Mg₃B₂N₄和Mg₃N₂触媒的异同。认为用常压合成的Mg₃B₂N₄作为初始触媒对于合成立方氮化硼是有利的。     

氢致LaMg2Ni合金薄膜的光电性能变化

采用电子束蒸发法沉积LaNi/Mg多层膜,再于350℃真空退火合金化的方法制备了厚度为375nm的LaMg₂Ni合金薄膜.在吸、放氢过程中,该合金薄膜能够在高反射的金属态和透明的半导体态之间可逆地转变.在可见光波长范围内的平均透射率和电阻率在反射态和透明态之间的对比度大于10⁴.利用扫描电子显微镜和原子力显微镜观察了吸放氢前后薄膜的表面及剖面形貌.结果表明,在氢化过程中薄膜表面的平整性降低且不可恢复,是脱氢态中出现低反射现象的主要原因. 关键词： 薄膜 光电性能 氢 形貌     

Splitting of a Cooper pair by a pair of Majorana bound states

We propose a method to probe the nonlocality of a pair of Majorana bound states by crossed Andreev reflection, which is the injection of an electron into one bound state followed by the emission of a hole by the other (equivalent to the splitting of a Cooper pair). We find that, at sufficiently low excitation energies, this nonlocal scattering process dominates over local Andreev reflection involving a single bound state. As a consequence, the low-temperature and low-frequency fluctuations deltaI(i) of currents into the two bound states i=1, 2 are maximally correlated: deltaI_1deltaI_2[over ]=deltaI_i(2).[over ].     

Ca8Mg(SiO4)4Cl2:Eu2+,Nd3+的近红外发光

用高温固相法制备了Ca<,8>Mg(SiO<,4>)<,4>Cl<,2>:Eu<'2+>,Nd<'3+>近红外发光材料,通过X射线衍射仪,近红外,可见发射光谱和激发光谱,荧光寿命等对样品进行了测试.研究了Eu<'2+>、Nd<'3+>的掺杂浓度对近红外发光性能的影响及相对强度变化的规律,结果表明,Ca<,8>Mg(Si...     

Analysis of the LIF Spectroscopy of Nickel Hydride in 19000-21400 cm-1

采用放电溅射出的镍原子与甲醇气体在超声射流条件下产生NiH分子,获得了NiH分子在15000~21400 cm-1的激光诱导荧光激发谱．首次报道了NiH分子在19000~21400 cm-1的光谱．将观测到的24个谱带归属到7个不同的电子跃迁,并对每个谱带进行了转动分析．观测到了A、B、D、E、F和G态的高振动能级,得到了这些电子态的振动频率、非谐性常数、转动常数和平衡键长等较完整的光谱常数．并重新标识了一些谱带．     

(Zn_(1-x),Mg_x)_2GeO_4∶Mn~(2+)的荧光以及长余辉发光性能

采用高温固相法制备了一系列(Zn_(1-x),Mg_x)_2GeO_4∶Mn~(2+)(0≤x≤0.25)绿色荧光粉,并研究了Mg离子对(Zn_(1-x),Mg_x)_2GeO_4∶Mn~(2+)的结构、荧光以及长余辉发光性能的影响。Mg离子取代Zn进入Zn_2GeO_4晶格,形成(Zn_(1-x),Mg_x)_2GeO_4固溶体,并产生了晶格畸变。光谱分析结果表明,样品中位于533 nm的绿色荧光源于Mn~(2+)的~4T_1(~4G)→~6A_1(~6S)跃迁。随着Mg离子浓度的增加,(Zn_(1-x),Mg_x)_2GeO_4∶Mn~(2+)样品的激发光谱出现了蓝移现象,说明Mg离子进入到Zn_2GeO_4晶格中对其晶格结构产生了影响,导致(Zn_(1-x),Mg_x)_2GeO_4的带宽发生改变。发射光谱则表明Mg离子进入Zn_2GeO_4晶格引起Mn~(2+)的~4T_1(~4G)→~6A_1(~6S)跃迁绿色荧光发光强度的增强。Zn_2GeO_4基质中的氧空位缺陷陷阱深度由于基质带宽的变化而变深,样品具有良好的长余辉发光效果。通过热释光谱分析研究了材料中缺陷陷阱的特征,进一步证实了(Zn_(1-x),Mg_x)_2GeO_4中缺陷陷阱深度发生改变。根据光谱分析结果给出了(Zn_(1-x),Mg_x)_2GeO_4∶Mn~(2+)中荧光与余辉发光的产生机理。     

(Mg1-x-yBaxSry)1.95SiO4∶0.05Eu荧光粉的光谱研究及紫外激发色像图建立

采用高温固相法制备了新型(Mg1-x-yBaxSry)1.95SiO4∶0.05Eu荧光粉,其中包括3个二元碱土离子配比系列和3个代表性三元碱土离子配比系列(Ba不变而Mg/Sr比连续变化、Mg/Sr比不变而Ba含量连续变化)共计6个系列,并研究其光谱性能(激发谱和发射谱)、紫外(254和365 nm)发光照相记录及CIE值对应色像。借鉴三元相图的建立思路,由这些二元和代表性三元数据推导三元色像图,用于新型荧光粉的系统开发。所制备的荧光粉系列包括:Mg2SiO4-Sr2SiO4,Ba2SiO4-Sr2SiO4,Mg2SiO4-Ba2SiO4,Ba原子比含量为0.2(Mg/Sr原子比连续变化),Ba原子比含量为0.6(Mg/Sr原子比连续变化),Mg/Sr原子比为1/4(Ba原子比含量连续变化系列)。其对应的254 nm激发下光谱性能、发光照相记录、和CIE色像分析表明:Eu离子可以三价和二价形式存在于(Mg1-x-yBaxSry)2SiO4中;二元系列中(Mg1-xBax)2SiO4和(Ba1-ySry)2SiO4基体中随着Ba原子比的增加荧光粉逐渐由红(对应Eu3+5D0→7F1和5D0→7F2电子跃迁窄带发射)变绿(对应Eu2+4fn-15d→4fn电子跃迁发射宽带发射)且前者变化的更快;二元系列中(Mg1-ySry)2SiO4系列为红色荧光粉,且随着Sr含量增加红色发光增大;三元系列中(Bax(Mg0.2Sr0.8)1-x)2SiO4(Mg/Sr=1/4)随着Ba离子量增加荧光粉也逐渐由红变绿,其变化速度介于Mg/Sr比等于0(即Ba2SiO4-Sr2SiO4系列)和Mg/Sr比等于∝(即Ba2SiO4-Mg2SiO4系列);三元系列中(Ba0.2SryMg0.8-y)1.95SiO4为红色荧光粉,而(Ba0.6SryMg0.4-y)2SiO4随着Mg/Sr原子比增加逐渐由红转蓝绿光。365 nm激发下荧光发射的变化规律与254 nm激发下大体一致,但是同一样品在365 nm激发下其绿光波段发射要比254 nm激发要强且其红光波段发射要比254nm激发要弱,故(Mg1-xBax)2SiO4,(Ba1-ySry)2SiO4,(Bax(Mg0.2Sr0.8)1-x)2中对应的由红变绿时Ba含量分别为40at%,60at%,60at%(254 nm激发下60at%,80at%,70at%)且(Ba0.6SryMg0.4-y)2SiO4中由红变绿的Mg/Sr比为1/4(254 nm激发下为2/3)。据此建立Eu掺杂Ba2SiO4-Mg2SiO4-Sr2SiO4紫外激发色像图。借由色像图可知(Mg1-x-yBaxSry)1.95SiO4∶0.05Eu荧光粉紫外激发下发射光变化规律,即基体组分靠近Ba2SiO4端发射绿色而靠近Mg2SiO4或Sr2SiO4端发射红色,Mg/Sr比越大随着Ba原子的增加荧光粉的由红转绿的速度越快;同一样品在365 nm激发下其绿光波段发射要比254 nm激发要强且其红光波段发射要比254 nm激发要弱,(Mg1-x-yBaxSry)1.95SiO4∶0.05Eu荧光粉中当Ba>80at%,Mg>90at%(或Sr>80at%)荧光粉可分别用作高效绿色、红色荧光粉;此外,当组分为(Mg0.8Sr0.2)1.95SiO4∶0.05Eu,(Ba0.8Mg0.16Sr0.04)1.95SiO4∶0.05Eu是紫外激发下(254和365 nm)最好的红色和绿色荧光粉。     

Flux conversion and evidence of relaxation in a high-beta plasma formed by high-speed injection into a mirror confinement structure

High-beta plasmoids can survive the violent dynamics of supersonic reflection off mirror structures, producing a stable high-beta field-reversed configuration (FRC). This shows both the robustness of FRCs and their tendency to assume a preferred plasma state, possibly conforming to a relaxation principle. The key observations are (1) approximate preservation of the magnetic helicity, (2) substantial conversion from toroidal to poloidal magnetic flux, (3) substantial toroidal flow, and (4) a high-beta quiescent final state. These results are from the Translation, Confinement, and Sustainment experiment where a disorganized plasmoid is injected at super-Alfvenic speed into a confinement chamber. After successive reflections from end mirrors, the plasmoid settled into a near-FRC state with high beta and low toroidal magnetic field. The flux conversion and helicity preservation are inferred by an interpretive model.     

The correlation timescale of the X-ray flux during the outbursts of soft X-ray transients

Recent studies of black hole and neutron star low mass X-ray binaries (LMXBs) show a positive correlation between the X-ray flux at which the low/hard(LH)-to-high/soft(HS) state transition occurs and the peak flux of the following HS state. By analyzing the data from the All Sky Monitor (ASM) onboard the Rossi X-ray Timing Explorer (RXTE), we show that the HS state flux after the source reaches its HS flux peak still correlates with the transition flux during soft X-ray transient (SXT) outbursts. By studying large outbursts or flares of GX 339-4, Aql X-1 and 4U 1705-44, we have found that the correlation holds up to 250, 40, and 50 d after the LH-to-HS state transition, respectively. These time scales correspond to the viscous time scale in a standard accretion disk around a stellar mass black hole or a neutron star at a radius of ∼10^4–5 R _g, indicating that the mass accretion rates in the accretion flow either correlate over a large range of radii at a given time or correlate over a long period of time at a given radius. If the accretion geometry is a two-flow geometry composed of a sub-Keplerian inflow or outflow and a disk flow in the LH state, the disk flow with a radius up to ∼10⁵ R _g would have contributed to the nearly instantaneous non-thermal radiation directly or indirectly, and therefore affects the time when the state transition occurs.

     

Interaction of a practical fluoran-based black color former with possible color developers, various acids and magnesium ions, in acetonitrile

For the purpose of improving the visible method of γ-rays detection, detailed conditions with various acids have been examined for the color development of a fluoran-based black color former in acetonitrile. It is suggested that the protons (H⁺), which may be produced from acid generators by γ-ray radiation, can be properly detected by the color development of the black color former containing proper kinds and concentrations of bases. Reversible decolorization through the interaction between Mg²⁺ and polyamines (acyclic and macrocyclic) has been examined in order to reconfirm that the colored zwitterion is produced by the direct chemical interaction with Mg (ClO₄)₂ in the fluoran dye–acetonitrile solution.     

Horizon state, Hawking radiation, and boundary Liouville model

We demonstrate that the near-horizon physics, the Hawking radiation, and the reflection off the radial potential barrier can be understood entirely within a conformal field theory picture in terms of one- and two-point functions in the boundary Liouville theory. An important element in this demonstration is the notion of horizon state, the Hawking radiation being interpreted as a result of the transition of horizon state to the ordinary states propagating outside the black hole horizon.