Vibrational spectra of Te(OH)6·X2SO4 (X = Tl,Na)

The IR and Raman spectra of Te(OH)₆·X₂SO₄ (X = Tl, Na) have been recorded and analysed. The splitting of the nondegenerate mode of the sulphate ion suggests factor group interaction between the vibrating ions. The linear distortion of the sulphate ions is found to be more in Te(OH)₆·Na₂SO₄ than in Te(OH)₆·Tl₂SO₄. The tellurate ion seems to be less distorted than the sulphate ion. The appearance of Raman inactive modes of the tellurate ion indicate the presence of strain produced by the crystalline field. The anions are also found to coexist independently.     

Time-dependent quantum wave packet and quasiclassical trajectory studies of the Au(2S) + H2(X1∑+g) → AuH(X1∑+g) + H(2S) reaction

The time-dependent quantum wave packet (TDWP) and quasiclassical trajectory calculations (QCT) are carried out for the Au(²S) + H₂(X¹∑⁺_g) → AuH(X¹∑⁺_g) + H(²S) reaction on a global potential energy surface. The reaction probabilities at a series of J values, integral cross sections (ICSs) and differential cross sections of the title reaction are calculated by the TDWP method. For reaction probabilities, there are a mass of sharp oscillations at low collision energy, which can be attributed to resonances supported by the potential well. Due to the endothermicity of the title reaction, the total ICS shows a threshold about 1.53 eV. In order to further investigate the reactive mechanism, the lifetime of complex is calculated by QCT method. At the low collision energy, most intermediate complexes are long lived, which implies that the reaction is governed by indirect reactive mechanism. With the collision energy increasing, the direct reactive mechanism occupies the dominant position. Due to the change of the reactive mechanism, the angular distribution shifts toward the forward direction with collision energy increasing. The isotopic variant, Au + D₂→AuD + D reaction, is also calculated by TDWP method. The calculated reaction probabilities and ICSs show that the isotope effect reduces the reactivity.     

用X射线旋进照相研究(Bi_(2-x)Pb_x)Sr_2CuO_y(0.1≤x≤0.6)晶体结构

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Vibrational and rotational excitation effects of the N(2D) + D2(X1Σg +) → ND(X3Σ+) + D(2S) reaction

The effects of the rovibrational excitation of reactants in the N(²D) + D₂(X¹Σ_g⁺) → ND(X³Σ⁺) + D(²S) reaction are calculated in a collision energy range from the threshold to 1.0 eV using the time-dependent wave packet approach and a second-order split operator. The reaction probability, integral cross-section, differential cross-section and rate constant of the title reaction are calculated. The integral cross-section and rate constant of the initial states v = 0, j = 0, 1, are in good agreement with experimental data available in the literature. The rotational excitation of the D₂ molecule has little effect on reaction probability, integral cross-section and the rate constant, but it increased the sideways and forward scattering signals. The vibrational excitation of the D₂ molecule reduced the threshold and broke up the forward–backward symmetry of the differential cross-section; it also increased the forward scattering signals. This may be because the vibrational excitation of the D₂ molecule reduced the lifetime of the intermediate complex.     

The quenching of excited F(2 P 1/2) and Cl(2 P 1/2) atoms by N2(X 1Σ g + ) molecules

The rate constant for the quenching of excited F(² P _1/2) and Cl(² P _1/2) atoms in collisions with N₂ molecules were calculated. The electron interaction matrix between N₂(X ¹Σ _g ⁺ ) and F and Cl atoms in the ² P _j state calculated asymptotically taking into account quadrupole-quadrupole, dispersion, and exchange interactions was used. The dynamic problem of electronic transitions was solved using the modified wave number approximation, the exactly solvable semiclassical exponential nonadiabatic bond model, and the method of phase functions.     

High-Resolution Spectroscopy of Jet-Cooled (32)SO(2) and (34)SO(2): The ã(3)B(1)-;X(1)A(1), 2(1)(0) and 1(1)(0) Bands

Laser-induced excitation spectra of the two bands ?(3)B(1)-;X(1)A(1), 2(1)(0) and 1(1)(0) of (32)SO(2) and (34)SO(2) have been recorded in a supersonic jet at a resolution of 0.015 cm(-1). The rotational and electron-spin fine structure has been analyzed for both isotopic species. Analysis of the rotational and electron-spin fine structure yields precise values of the rotational constants A, B, and C and the spin constants alpha and beta for both (32)SO(2) and (34)SO(2) in the states ?(3)B(1) (010) and (100). No interaction between these two vibrational states with any nearby triplet state is observed for rotational levels with J 相似文献   

(XB2)2(X=Al, Be, Na, Mg)团簇的密度泛函研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G*基组水平上对(XB2)2(X=Al,Be,Na,Mg)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.并对最稳定结构的电子结构、振动特性、成键特性和电荷特性等进行了理论研究.结果表明,团簇的几何结构大多是平面结构,通常是B-B键和B-X键共存,较少出现X-X键.团簇的稳定结构中通常是几个呈负电性的B原子形成一个负电中心,而其他B原子和X原子处在端位,且显正电性.     

OH分子基态(X2Ⅱ)的结构与势能函数

采用密度泛函理论的B3LYP方法和二次组态相互作用(QCISD(T))方法优化计算了OH分子基态(X2Ⅱ)的平衡结构、振动频率和离解能.根据原子分子反应静力学原理,导出了OH分子基态(X2Ⅱ)的合理离解极限,采用最小二乘法拟合Murrell-Sorbie函数得到了相应的势能函数和与该基态相对应的光谱常数(Be,αe,ωe和ωe xe),计算结果与实验数据符合得相当好.     

Vibrational analysis of the (B 2 П→X 2 П) system of NS

A few red degraded bands attributable to NS have been reported earlier byFowler andBarker, Dressler andBarrow et al, and they occur in the same region (2300 to 2700 Å) as the bands of the known systems (C ² ∑ ⁺?X ² П) and (A ² Δ?X ² П). Measurements made on the heads of some of these weak bands ledBarrow et al. to believe that these bands may form a system analogous to theβ-system of NO and be due to a² П-² П transition. The spectrum of NS has now been studied in a little more detail by means of an uncondensed discharge through dry nitrogen and sulphur vapour in the presence of argon and thirty three bands belonging to this system have been recorded in the region 2280 to 2760 Å. It has been found possible to represent the band heads by means of the equation

$$^v {\text{head}} {\text{ = }} \left. {_{43182 \cdot 5}^{{\text{43311}} \cdot {\text{5}}} } \right\}_{ - [1219 \cdot 20(v'' + \tfrac{1}{2}) - 7 \cdot 48(v'' + \tfrac{1}{2})^2 ].}^{ + [761 \cdot 04(v' + \tfrac{1}{2}) - 5 \cdot 10(v' + \tfrac{1}{2})^2 ]}$$     

HX+2(X=Cl,Br)离子的密度函数理论(DFT)研究

选取密度泛函方法,采取6-311++G(2df,2pd)基组对单态HCl+2和HBr+2离子进行了理论计算.考虑到HF+2离子中D∞h结构可独立存在的事实,文中首次对HCl+2和HBr+2离子的包含D∞h在内的四种可能几何构型进行了优化计算;求得了Cl2与Br2的质子亲和能及Cl-ClH+与Br-BrH+的键分离能,丰富和完善了对HCl+2的理论计算,并对HBr+2离子存在的可能性进行了计算研究,结果预言HBr+2单态中Cs结构为其平衡结构.最后给出了HCl+2和HBr+2的热化学数据、力常数等数值,并给出了基态HBr+2离子的离解通道,从而给出其完全离解时的离解能,为该离子的分析势能函数的推导准备了必需的理论数据.     

RRKM理论研究N(4S)+CH2X(X=F,Cl)的反应通道

采用RRKM理论和疏松过渡态模型计算了N(4S) +CH2 X(X =F ,Cl)反应的微正则速率常数和通道分支比 .计算结果表明 ,在较低的内能下 (E =2 80 .2 9kJ/mol) ,N(4S) +CH2 F的主要产物为NCHF +H ,占总产物的5 9.2 % ,次要产物为H2 CN +F ,占 37.4 % .而N(4S) +CH2 Cl反应在E =2 6 7.78kJ/mol时 ,主要产物是H2 CN +Cl,占 90 .3% ,NCHCl+H只占 9.0 % .在内能较高的时候 (取E =5 0 0 .0 0kJ/mol) ,N(4S) +CH2 F的主要通道并未变化 ,而N(4S) +CH2 Cl的主要通道变为NCHCl+H ,比例为 5 1.5 % ,H2 CN +Cl的比例降到 4 0 .4 % .     

CaAl2X2(X=C,Si,Ge)的稳定性、电子结构和力学性质研究

由于AB2X2类型的材料在储能、催化、超导、发光等领域都有着潜在应用价值,因此得到了广泛关注。本文通过第一原理方法计算分析了CaAl2X2(X=C,Si,Ge)的材料声子谱、电子结构、力学性质和硬度,其主要结果为：材料晶格常数的计算结果和实验值都与理论结构符合的很好;CaAl2C2和CaAl2Si2材料的声子谱没有出现虚频,表明这两种材料在热力学及动力学上是稳定的;计算的材料的能带结构表明,CaAl2Si2和 CaAl2Ge2具有金属特性, CaAl2C2具有较小带隙的间接半导体材料。这类材料的金属特性,热稳定性及力学各项异性特征对于其作为二次电池活性电极有着重要影响,因此本文的研究结果可为相关领域的研究提供较好的理论依据及参考。     

n-C_(16)H_(33)NH_3X和(n-C_(16)H_(33)NH_3)_2MX_4的红外光谱研究

在室温和液氮温度下研究了(n-C_(16)H_(33)NH_3)_2MX_4(简称C_(16)MX)及其相应化合物n-C_(16)H_(33)NH_3X(简称C_(16)X)于4000～50cm~(-1)范围的红外光谱。结果表明,它们都形成N-H…X型氢键,氢键强度是C_(16)X大于C_(16)MX。后者氢键的强度是按Cl>Br>I的顺序递减。C_(16)MX的光谱性质可按金属离子性质分为Cu~(2+)(Cu~(2+)、Cd~(2+)、Mn~(2+))和Zn~(2+)(Zn~(2+)、Co~(2+))两组,阴离子配位多面体的形状对其光谱性质有明显影响。还比较了室温与低温下的远红外光谱,证明了M—X键是离子键。     

气相反应N(4S)+O2(X3∑g-)→NO(X2Π)+O(3P)的准经典轨线研究

基于从头算数据拟合得到的新的基态势能面,对气相反应N(4S) O2(X3∑g-)→NO(X2Π) O(3P)进行了系统的准经典轨线研究.文中计算了该反应的反应几率、反应截面以及在T=300、500、700 K时的热速率常数.通过与以前的理论值和实验值比较发现,我们算得的结果与实验值符合得很好.     

H2Se(X1A1)分子的解析势能函数

使用密度泛函B3LYP方法和 6-311++G**基组,在优化H2Se(X1A1)基态结构,确定其正确离解极限,计算所有两体项和三体项参数基础上,建立了H2Se(X1A1)的多体项展式解析势能函数。其中对处于激发态两体项HSe(A2∑+)的计算,则使用SAC-CI方法。H2Se(X1A1)的等值势能图准确地表现了其结构和势能面的特征。     

Intensity anomaly in the A2∑+←X2∏ resonant-(2+2) multiphoton ionization spectra of NO

The two-photon resonant four-photon ionization spectra of NO via A²⁺X² (v=0,1) states have been measured. Some intensity-anomalous lines have been found. Based on the signal-power dependence measurement for the normal and anomalous lines, a double resonance and collision ionization model is suggested to elucidate the intensity anomaly.     

Can X(3872) be a JP=2- Tetraquark State?

In this article, we test the nature of X(3872), which is assumed to be a P-wave [cq]-scalar-diquark [cq]-axial-vector-antidiquark tetraquark state with J^P=2^-. The interpolating current representing the J^P=2^- state is proposed. Technically, contributions of the operators up to dimension six are included in the operator product expansion. The mass obtained for such state is m_2-=(4.38? 0.15) GeV. We conclude that it is impossible to describe the X(3872) structure as J^P=2^- tetraquark state.     

BaMgAl_(10)O_(17)∶Eu~(2 )的MgF_2表面包覆(英文)

采用溶胶-凝胶法对蓝色荧光粉BaMgAl10O17∶Eu2 (BAM)进行表面包膜处理,获得了表面均匀包覆MgF2膜层的BAM荧光粉。并用SEM、XRD和IR手段对其表面形貌、晶格结构性能进行了表征;用EDS对BAM粉体的表面元素进行了定性分析;用荧光光谱测试对荧光粉的发光性能进行了研究。结果表明,在BAM粉体表面均匀包覆MgF2层后,BAM的晶格结构,发光性能没有改变,初始亮度较未包覆的荧光粉有所降低,经过相同条件的热处理后,包覆MgF2荧光粉的亮度热衰减程度明显低于未包覆的荧光粉,且色坐标偏移现象不明显。     

High-level ab initio studies of NO(X2Π)–O2(X3Σg −) van der Waals complexes in quartet states

Geometry optimisations were performed on nine different structures of NO(X²Π)–O₂(X³Σ_g^?) van der Waals complexes in their quartet states, using the explicitly correlated RCCSD(T)-F12b method with basis sets up to the cc-pVQZ-F12 level. For the most stable configurations, counterpoise-corrected optimisations as well as extrapolations to the complete basis set (CBS) were performed. The X structure in the ⁴A′ state was found to be most stable, with a CBS binding energy of ?157 cm^?1. The slipped tilted structures with N closer to O₂ (Slipt-N), as well as the slipped parallel structure with O of NO closer to O₂ (Slipp-O) in ⁴A″ states have binding energies of about ?130 cm^?1. C_2v and linear complexes are less stable. According to calculated harmonic frequencies, the X isomer is bound. Isotropic hyperfine coupling constants of the complex are compared with those of the monomers.