Aun(n=2,3,4)团簇与乙醇分子相互作用的第一性原理研究

利用密度泛函理论研究了Au_n(n=2,3,4)团簇与乙醇分子的吸附机理.研究结果表明:Au_n(n=2,3,4)团簇分别能够吸附1到n个乙醇分子,生成Au_n-(C₂H₆O)_1-n配合物;Au₄团簇吸附乙醇分子有多种构型,通过分析吸附能和Mulliken电荷分布,确定了4个乙醇分子的吸附顺序及相应的稳定构型;Au_n(n=3,4)团簇在吸附最后一个乙醇分子时改变了前面Au—O成键的作用模式,而是选择Au—H成键;作为吸附主体的金团簇和被吸附的乙醇分子在吸附前后构型变化都很少,它们之间的吸附作用为弱相互作用. 关键词： 金团簇 乙醇分子 密度泛函理论     

［Mg(NH2)2］n(n=1—5)团簇的密度泛函理论研究

用密度泛函理论的杂化密度泛函B3LYP方法在6-31G^*基组水平上对［Mg(NH₂)₂］_n(n=1—5)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.对最稳定结构的振动特性、成键特性、电荷特性等进行了理论研究.结果表明：团簇易形成链状结构,Mg—N键长为0.190—0.234 nm,N—H键长为0.101—0.103 nm,H—N—H键角为100.2°—107.5°;团簇中M 关键词： 2)₂］_n(n=1—5)团簇')" href="#">［Mg(NH₂)₂］_n(n=1—5)团簇 密度泛函理论 结构与性质 储氢材料     

AlHn(n=1—3)的分子结构和AlH3热力学稳定性

在gaussian03基础上，分别用b3lyp和qcisd方法，在6-311++g^**基组水平上研究了AlH_n(n=1—3)分子及其一价阴阳离子的几何结构和谐振频率，计算了它们中性分子的离解能，第一垂直电离能，电子亲和能. 并与可能得到的实验值及文献上的理论计算值进行了比较. 发现qcisd方法得到的数据更接近实验值. 计算发现对AlH，AlH₂和AlH₃分子及其1价阳离子的Al—H键长，随着H原子数的增多，键长越短， 关键词： 3分子')" href="#">AlH₃分子 平衡几何结构 垂直电离能 垂直电子亲和能     

单母体遗传算法优化(H2O)n(n≤14)的结构

在传统遗传算法的基础上提出了单母体遗传算法(single-parent genetic algorithm, SPGA)，通过对母体团簇实施两种不同的变异操作对结构进行优化，给出了分子团簇结构优化的算法实现. 结合TIP3P模型势函数，研究了水分子团簇(H₂O)_n(n≤14)的稳定结构. 优化结构和已有理论及实验结果一致. 计算结果表明当n<8时，平均结合能随n增加较快；当n≥8时有小的起伏. n=4,8,10,12的团簇结构具有较高对称性，比较稳定. 关键词： 单母体遗传算法 水分子团簇 结构优化     

(TiO2)n(n=3—6)团簇吸附水分子的理论研究

给出了优化小分子在团簇表面吸附结构的遗传算法.结合经验势函数,搜寻了水分子在(TiO₂)_n(n=3—6)团簇上可能的吸附方式;利用B3LYP/6-31G^**方法对各种吸附结构进行了优化.结果表明水分子主要通过O原子以非解离方式吸附到团簇中配位数较低或位置比较凸出的Ti原子上.分子轨道分析表明,水分子与团簇之间的成键主要来自吸附位Ti原子3s3p轨道的贡献,水分子的轨道保持了气相水分子中的基本特征,但离域化程度增大 关键词： 2团簇')" href="#">TiO₂团簇 2O吸附')" href="#">H₂O吸附 遗传算法 DFT     

Laser spectroscopy of the thallium atom based on transitions 6 p 1/2 → 6 D 3/2 → nF 5/2 ( n = 13–24)

The energies and quantum defects of Rydberg states nF _5/2 (n = 13–24) of the thallium atom have been studied experimentally. The Rydberg states were excited from the ground state 6² P _1/2 by the two-stage scheme through the intermediate state 6² D _3/2. By using a collimated atomic beam and monochromatic radiation of two narrow-band tunable lasers, we have succeeded in resolving the hyperfine and isotopic structures of the ground state of the thallium atom and in determining the energy positions of the states nF _5/2 accurate to 0.03 cm⁻¹, which exceeds the accuracy achieved in the previous works by more than an order of magnitude. The quantum defect of nF _5/2 states is independent of n within the measurement accuracy and is equal to Δ = 1.0344 ± 0.0008. The ionization potential I _p = 49266.55 ± 0.03 cm⁻¹ has been found for the ²⁰⁵Tl isotope from the level 6² P _1/2 (F = 0). The energy of the 6² D _3/2 level measured experimentally relative to the state F = 0 of the 205 isotope amounted to 36118.56 ± 0.02 cm⁻¹. Original Russian Text ? P.A. Bokhan, Dm.E. Zakrevskii, V.A. Kim, N.V. Fateev, 2008, published in Optika i Spektroskopiya, 2008, Vol. 104, No. 5, pp. 771–776.     

(Ca3N2)n(n=1—4)团簇结构与性质的密度泛函理论研究

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(Ca₃N₂)_n(n=1—4)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.并对最稳定结构的振动特性、成键特性、电荷特性和稳定性等进行了理论分析.结果表明,(Ca₃N₂)_n(n=1—4)团簇最稳定构型中N原子为3—5配位,Ca—N键长为0.231—0.251nm,Ca—Ca键长为0.295—0.358nm;N原子的自然电荷在-1.553e—-2.241e之间,Ca原子的自然电荷在1.035e—1.445e之间,Ca和N原子间相互作用呈现较强的离子性,Ca₃N₂和(Ca₃N₂)₃团簇有相对较高的动力学稳定性. 关键词： 3N₂)_n(n=1—4)团簇')" href="#">(Ca₃N₂)_n(n=1—4)团簇 密度泛函理论 结构与性质     

宽带非均匀半径渐变TE0n-TE0(n+1)模式转换器的设计研究

基于耦合波理论,对两类半径渐变圆波导TE_0n-TE_0(n+1)模式转换器进行理论分析、数值计算和仿真模拟.均匀半径渐变波导高功率模式转换器,采用中心频率为17.14GHz、六周期TE₀₂-TE₀₃模式和中心频率为34.30GHz、六周期TE₀₁-TE₀₂模式两种设计参数.非均匀半径渐变波导高功率模式转换器,采用中心频率为34.30GHz、六周期TE 关键词： 模式转换器 耦合波理论 非均匀半径渐变 转换带宽     

CnH2n(n=2,3,4)与BX3(X=H,F,Cl)作用的DFT研究

用量子化学的密度泛函理论方法对BX     

CrHn(n=0,+1,+2)分子及离子的势能函数

用原子分子反应静力学原理推导出CrHⁿ(n=0，+1，+2)的电子状态及其离解极限. 对H原子采用6-311++G^**基组，对Cr原子采用SVP(split valence polarization)全电子基组，用B3PW91方法计算了它们的平衡几何、电子状态，在此基础上分别计算CrH，CrH⁺的Murrell-Sorbie解析势能函数和CrH²⁺的解析势能函数及其对应的力常数、光谱参数，理论计算值与实验值和文献计算值符合较好. 从离解极限和通道解释了不同的势能函数形状. 计算表明：CrH⁺的势能曲线均具有对应于稳定平衡结构的极小点，说明CrH⁺可稳定存在. 而CrH²⁺离子的势能曲线对应于不稳定的排斥态，说明CrH²⁺是不稳定的. 关键词： n(n=0')" href="#">CrHⁿ(n=0 +2) 势能函数 光谱参数 稳定性     

Orbital responses to methyl sites in CnH2n+2 (n=1-6)

Orbital responses to methyl sites in C_nH_2n+2 (n=1-6) are studied by B3LYP/TZVP based on the most stable geometries using the B3LYP/aug-cc-pVTZ method. Vertical ionization energies are produced using the SAOP/et-pVQZ model for the complete valence space. The highest occupied molecular orbital (HOMO) investigations indicate the p-electron profiles in methane, ethane, propane, and n-butane. By increasing the number of carbon-carbon bonds in lower momentum regions, the s, p-hybridized orbitals are built and display strong exchange and correlation interactions in lower momentum space (P≤0.50 a.u.). Meanwhile, the relative intensities of the isomers in lower momentum space show the strong bonding number dependence of the carbon-carbon bonds, meaning that more electrons have contributed to orbital construction. The study of representative valence orbital momentum distribution further confirms that the structural changes lead to evident electronic rearrangement over the whole valence space. An analysis based on the isomers reveals that the valence orbitals are isomer-dependent and the valence ionization energy experiences an apparent shift in the inner valence space. However, such shifts are greatly reduced in the outer valence space. Meanwhile, the opposite energy shift trend is found in the intermediate valence space.     

Synthesis and luminescence properties of lead-halide based organic–inorganic layered perovskite compounds (CnH2n+1NH3)2PbI4 (n=4, 5, 7, 8 and 9)

This paper describes the synthesis and characterization of organic–inorganic layered perovskite compounds, (C_nH_2n+1NH₃)₂PbI₄ (n=4, 5, 7, 8 and 9). The effect of the number of carbon atoms on luminescence properties has been examined. Thin films of microcrystalline (C_nH_2n+1NH₃)₂PbI₄ fabricated by spin-coating are highly oriented, with the c-axis perpendicular to the substrate surface. Temperature-dependent optical absorption spectra reveal that (C_nH_2n+1NH₃)₂PbI₄ films (n=4, 7, 8 and 9) show the structural phase transitions. The excitonic structures of (C_nH_2n+1NH₃)₂PbI₄ vary with the number of carbon atoms of the alkyl chain length. At low temperatures below 100 K, the lowest-energy free-exciton band of (C_nH_2n+1NH₃)₂PbI₄ (n=7, 8 and 9) split into three fine-structure levels. In contrast to (C_nH_2n+1NH₃)₂PbBr₄ films, (C_nH_2n+1NH₃)₂PbI₄ (n=7, 8 and 9) shows no triplet exciton emission, but it shows the Stokes-shifted emission from bound excitons.     

Raman study of HgBa2Can−1CunO2n+2+δ (n=1,2,3,4 and 5) superconductors

Polarized micro-Raman scattering measurements have been performed on the five members of the HgBa₂Ca_n−1Cu_nO_2n+2+δ (n=1,2,3,4 and 5) high-T_c superconductor family using different laser frequencies. Local laser annealing measurements were carried out to investigate the variation of the Raman spectra with the excess oxygen content, δ. A systematic evolution of the spectra, which display mainly peaks near 590, 570, 540 and 470 cm⁻¹, with increasing number of CuO₂ layers has been observed; its origin has been shown to lie in the variation of the interstitial oxygen content. In addition to confirming that the 590 cm⁻¹ mode represents vibration of apical oxygens in the absence of neighboring excess oxygen, the 570 cm⁻¹ mode, which may be composed of some finer structures, has been assigned to the vibration of the apical oxygen modified by the presence of the neighboring excess oxygens. The 540 and 470 cm⁻¹ modes may represent the direct vibration of excess oxygens. The implication of possible different distribution sites of excess oxygens is discussed. All other observed lower-frequency modes are also assigned.     

Screening influence on the Stark effect of impurity states in strained wurtzite GaN/AlxGa1-xN heterojunctions under pressure

The screening effect of the random-phase-approximation on the states of shallow donor impurities in free strained wurtzite GaN/Al x Ga 1 x N heterojunctions under hydrostatic pressure and an external electric field is investigated by using a variational method and a simplified coherent potential approximation.The variations of Stark energy shift with electric field,impurity position,Al component and areal electron density are discussed.Our results show that the screening dramatically reduces both the blue and red shifts as well as the binding energies of impurity states.For a given impurity position,the change in binding energy is more sensitive to the increase in hydrostatic pressure in the presence of the screening effect than that in the absence of the screening effect.The weakening of the blue and red shifts,induced by the screening effect,strengthens gradually with the increase of electric field.Furthermore,the screening effect weakens the mixture crystal effect,thereby influencing the Stark effect.The screening effect strengthens the influence of energy band bending on binding energy due to the areal electron density.     

光学偶极阱中铷原子5S_(1/2)及5P_(3/2)态的AC Stark频移

基于二能级模型和多能级模型,分析计算了由强聚焦高斯光束形成的光学偶极阱中87Rb原子5S1/2态和5P3/2态的AC Stark频移。基于多能级模型,针对在852 nm高斯激光束强聚焦所形成的87Rb原子远失谐光学偶极阱中进行偏振梯度冷却的情形,计算了冷却循环跃迁(5S1/2F=2-5P3/2F′=3)的频移量,结果显示频移对molasses冷却过程产生了重要的影响。同时,计算了5S1/2|F=2,mF=±2〉态和5P3/2|F′=3,mF=±3〉态的AC Stark频移随光学偶极阱激光波长的变化情况,发现在红失谐情况下,对于87Rb原子5S1/2-5P3/2态跃迁不存在魔数波长。     

Density functional study of Agn-1Y (n=2-10) clusters

Employing the density functional theory, we investigate the lowest-energy geometric, the stable and the electronic properties of Ag_n-1Y (n=2-10) clusters in this paper. The structural optimization and the frequency analysis are performed at the B3LYP/LANL2DZ level. Meanwhile, the differences in geometry, stability and electronic properties between Ag_n and Ag_n-1Y (n=2-10) clusters are also studied. The results show that for the doping of the yttrium atoms, the structures and the average binding lengths of the Ag_n clusters are greatly changed. In addition, the thermodynamic stabilities of the Ag_n clusters are enhanced generally with the doping of the Y atoms. In addition, the chemical stabilities of the Ag_n-1Y clusters are still improved compared with that of the three-dimensional Ag_n clusters.     

Local environment of fluorine atoms in Sr2Can ? 1CunO2n + δF2 ± y (n = 2, 3) high-temperature superconductors grown under high pressure

The local environment of fluorine atoms in Sr₂Ca _{n − 1}Cu _n O_{2n + δ}F_{2 ± y} (n = 2, 3) high-temperature superconductors (T _c = 99 and 111 K) is studied using soft x-ray emission and absorption spectroscopy. The fluorine spectra of the samples studied are found to be similar to those of SrF2, which supports the conjecture that fluorine atoms substitute for apex oxygen atoms and form double SrF layers. __________ Translated from Fizika Tverdogo Tela, Vol. 47, No. 7, 2005, pp. 1170–1174. Original Russian Text Copyright ? 2005 by Kurmaev, Moewes, Wilks, Nechkina, Zatsepin, Kawashima, Takayama-Muromachi.     

Synthesis and characterization of HgBa2Can−1CunO2n+2+δ (n = 1, 2, and 3)

We have successfully prepared the first three members of the mercury-based superconducting compounds Hg--- Ba₂Ca_n−1Cu_nO_2n+2+δ, namely Hg---1201, Hg---1212 and Hg---1223 with high purity and very good quality. T he influence of the synthesis parameters is studied in detail. Using the sealed quartz tube method, very simple procedures are found to ensure a 100% reproducibility of nearly 100% pure Hg---1201 and 85–90% Hg---1212 and Hg---1223. Oxygen annealing of the sample Hg---1201 at 300°C for 18 h results in an enhancement of its critical temperature up to 97 K. The symmetry of the first and second members is tetragonal with lattice parameters

Full-size image (2K)

, respectively. X-ray diffraction lines of Hg---1223 can be indexed in a tetragonal cell with

Full-size image (1K)

as well as in an orthorhombic cell with lattice parameters

Full-size image (1K)

.     

Electron impact ionization of Ar n , (H2O) n , Ar n (H2O) m clusters

Signals from ions forming in a supersonic molecular beam consisting of an argon-water vapor mixture are measured as functions of the exciting electron energy in the range to 120 eV. The thresholds of electron impact excitation of (H₂O) _{n − 1}H⁺ and Ar _n (H₂O _m ⁺ clusters are determined for the first time. It is found that the proton-hydroxyl group binding energy decreases considerably both in the case of water molecule clustering and when mixed Ar _n (H₂O) _m clusters arise.     

Synthesis and characterization of HgBa2Can−1CunO2n+2+δ (n = 1, 2, and 3)

We have successfully prepared the first three members of the mercury-based superconducting compounds Hg--- Ba₂Ca_n−1Cu_nO_2n+2+δ, namely Hg---1201, Hg---1212 and Hg---1223 with high purity and very good quality. T he influence of the synthesis parameters is studied in detail. Using the sealed quartz tube method, very simple procedures are found to ensure a 100% reproducibility of nearly 100% pure Hg---1201 and 85–90% Hg---1212 and Hg---1223. Oxygen annealing of the sample Hg---1201 at 300°C for 18 h results in an enhancement of its critical temperature up to 97 K. The symmetry of the first and second members is tetragonal with lattice parameters a = 3.8831 (1) Å, C = 9.5357 (2) Å, and A = 3.8624 (1) Å, C = 12.7045 (2) Å, respectively. X-ray diffraction lines of Hg---1223 can be indexed in a tetragonal cell with a = 3.8564 (1) Å and C = 15.8564 (9) Å as well as in an orthorhombic cell with lattice parameters a = 5.4537 (1) Å, B = 5.4247 (1) Å, and C = 15.8505 (7) Å.