Mn5Ge2.7M0.3 (M=Ga，Al，Sn) 化合物的磁性和磁熵变

研究了Mn₅Ge_2.7M_0.3(M=Ga，Al，Sn)化合物的磁性和磁熵变. x射线衍射实验表明，研究的化合物均呈六角Mn₅Si₃型结构. 三种原子对Ge原子的替代，使得平均Mn原子磁矩下降，但居里温度没有明显的变化. 由于磁矩的降低，导致磁熵变值的下降，在磁场变化为4.0×10⁶A·m^-1时，对应于M=Ga，Al和Sn的样品，最大磁熵变值ΔS^max_Ｍ分别为6.1，6.3和5.3J·kg^-1K^-1，但磁熵变峰值的半高宽ΔＴ_ＦＷＨＭ有所增加. 另外，Mn₅Ge_2.7M_0.3(M=Ga，Al，Sn)化合物在高于居里温度的Arrott曲线上出现了一个不连续点，即样品在一定温度下的顺磁磁化率在某一临界磁场下发生了突变，临界磁场与温度几乎呈正比关系.这可能是由于样品在加一定磁场时3d带的费米能级发生了变化，使得有效电子数的减少所致. 关键词： 居里温度 平均Mn原子磁矩 磁熵变 Arrott图     

稀有气体化合物MRg+和MRgF(M=Co，Rh，Ir，Rg=Ar，Kr，Xe)的成键分析

本文运用B3LYP、MP2、MP4(SDQ)和CCSD(T)方法对由稀有气体原子(Ar,Kr,Xe)与过渡金属原子(Co,Rh,Ir)形成的化合物MRg⁺和MRgF进行了几何结构优化和频率计算,并探究了这些化合物的热力学性质. 结果表明,MRg⁺在热力学上是稳定的,而MRgF在热力学上为亚稳态. 同时使用分子中的原子理论的电子密度拓扑分析方法、自然键轨道分析方法、能量分解分析方法等多种分析方法来解析M-Rg的成键性质. 结果显示,化合物 MRg⁺的单位正电荷主要分布在金属M上,且这类化合物中金属的电子密度分布与单价离子M⁺相似,因此MRg⁺中的M-Rg键弱且不共价. 与MRg⁺相比,MRgF中的M-Rg键长更短(接近于M与Rg原子的理论共价半径之和),Wiberg键级指数更大,具有部分共价性质.     

Xe原子偶宇称5p5(2P1/2)nl' [K']J (l'=1, 3)自电离态共振增强激发光谱线形研究

利用脉冲直流放电技术制备的Xe原子亚稳态5p⁵6s[3/2]₂和5p⁵6s'[1/2]₀, 在单光子为28000～42000 cm^-1能量范围内, 结合飞行时间质谱技术获得Xe原子5p⁵np'[3/2]₁,[1/2]₁和5p⁵nf'[5/2]₃自电离Rydberg态的共振增强激发光谱. 根据Fano线形公式对呈现明显不对称线形的激发谱进行系统地分析,获得系统的能级位置、量子亏损、线性因子、共振宽度、共振态寿命和衰减宽度等数据,其中线形因子和共振宽度相对有效量子数呈线性关系. 另外分析了5p⁵np'序列的能级间距.     

高效磷光[Ru(terpy)(phen)X]+配合物结构和光谱性质的理论研究

采用密度泛函方法研究了三个混合配体的Ru(II)配合物[Ru(terpy)(phen)X]⁺ (terpy为2,2',6',20'-三联吡啶,phen为1,10-邻二氮杂菲,X为-C≡CH (1)、Cl (2)和CN(3))的几何结构、电子结构和光谱性质．分别在B3LYP/LanL2DZ UB3LYP/LanL2DZ水平下优化了它们的基态和激发态结构．在TD-DFT计算水平下结合极化连续介质模型得到了它们在CH3CN溶液中的吸收和发射光谱．计算得到的Ru-C、Ru-N和Ru-Cl基态     

质谱和拉曼光谱对[M(H2O)n]+(M=Li,K)水合团簇的研究

采用质谱、拉曼光谱及理论计算对[M(H₂O)_n]+(M=Li,K)水合团簇进行了研究。质谱分析[M(H₂O)_n]+(M=Li,K)水合团簇的离子峰,推测其水溶液中最大水化数为12和13。采用拉曼光谱对浓度梯度相同的LiCl和KCl水溶液进行了讨论与比较,Li+和K+的水化作用导致~3 208 cm-1水结构拉曼峰发生了明显的变化,其中LiCl和KCl溶液的浓度分别在0~2.0和0~2.5 mol·L-1范围内,水化作用呈线性增强,浓度大于2.0和2.5 mol·L-1时,偏离线性关系,出现缔合。理论计算[M(H₂O)_n]+水合团簇结构和理论拉曼光谱表明,Li+,K+分别在n>4和n>6开始第二水化层,O-H伸缩振动频率发生了蓝移,氢键结构遭到了破坏,与实验结果一致。     

Ar原子偶宇称3p5(2P1/2)nl'[K']J(l'=1,3)自电离态激发谱线形研究

The even-parity autoionizing resonance series 3p⁵np''[3/2]_1,2, 3p⁵np''[1/2]₁, and 3p⁵nf''[5/2]₃ of Ar have been investigated exciting from the two metastable states 3p⁵4s[3/2]₂ and 3p⁵4s''[1/2]₀ in the photon energy range of 32500-35600 cm^-1 with an experimental bandwidth of ~0.1 cm^-1. The excitation spectra of the even-parity autoionizing resonance series show typical asymmetric line shapes. New level energies, quantum defects, line profile index and resonance widths, resonance lifetime and reduced widths of the autoionizing resonances are derived by a Fano-type line-shape analysis. The line profile index q and the resonance widths Γ are shown to be approximately proportional to the effective principal quantum number n^*. The line separation of the 3p⁵np'' autoionizing resonances is discussed.     

[Ru(MeIm)4L]2+ (L=iip, tip, 2ntz)的电子结构、DNA-键合、构效关系及光谱特征

采用密度泛函的方法,结合导体极化连续模型研究了水溶性二价钌-甲基咪唑类配合物[Ru(MeIm)₄iip]²⁺ (1)、[Ru(MeIm)₄tip]²⁺(2)和[Ru(MeIm)₄2ntz]²⁺ (3)的电子结构、DNA的键合倾向及构效关系．在水溶液中几何优化的基础上分析了配合物的电子结构特征,并合理解释了配合物与DNA的键合倾向．计算结果表明,在主配体上用噻吩代替咪唑取代基可以有效提高配合物与DNA的键合力;同时,在主配体的骨架上引入强电负性的N原子及NO₂基团可以明显降低配合物最低未占据分子轨道能量及前沿分子轨道能量差．基于以上计算结果,预测所设计的配合物3具有最大的DNA键合力常数．另外,详细分析了配合物1、2的构效关系及抗肿瘤作用机理,并预测了配合物3的抗肿瘤活性．最后,用含时密度泛函方法对配合物的电子吸收光谱进行了计算和模拟,并与实验结果进行了对比分析.     

Vibrational study of layered ZnPS3 compounds intercalated with [Co(η5 -C5H5)2+] and [Cr(η6 -C6H6)2+] CATIONS

Infrared and Raman spectra (10–3100 cm^?1) of the layered ZnPSs compound and of intercalates with [Co(η⁵ ? C₅H₅)₂⁺] and [Cr(η⁶ ? C₆H₆)₂⁺] cations in the polycrystalline state have been recorded 300–10 K temperature range. A complete assignment of the spectra is proposed in terms of PSs group motions, Zn²⁺ ion translations and [Co(η⁵ ? C₅H₅)₂⁺] or [Cr(η⁶ ? C₆H₆)₂⁺] internal vibrations. New low frequency for the [Co(η⁵-C₅H₅)₂⁺] intercalate at low temperature are assigned to librational and torsional modes of C₅H₅ rings. Moreover, the preresonance Raman spectra of this intercalate show a selective enhancement for the metal-ligand vibrations when the charge transfer band of the cobalticenium is approached. One concludes that guest molecules are intercalated under their cationic form, are weakly interacting with the host lattice and seem to be dynamically disordered at room temperature.     

Electronic structure of Sc2AC (A=Al, Ga, In, Tl)

Using ab initio calculations, we have studied Sc₂AC with A=Al, Ga, In and Tl. We show that C 2p and Sc 3d as well as A p and Sc 3d states are hybridized, but the antibonding states in the vicinity of the Fermi level weaken the overall bonding. In terms of the chemical bonding, the influence of the size of the A element is minute. Furthermore, the bulk modulus of the corresponding binary transition metal carbide is not conserved in these phases. Therefore, Sc₂AC can be classified as weakly coupled MAX phases according to Sun and co-workers [Z. Sun, D. Music, R. Ahuja, S. Li, J.M. Schneider, Phys. Rev. B 70 (2004) 092102]. It is our ambition that these calculations will stimulate experimental research on these compounds.     

HC2nO+ (n=3-6) 正离子的红外光解离光谱以及理论计算研究

本文利用脉冲激光溅射-超声分子束载带离子源在气相中产生了HC_2nO⁺ (n=3-6)正离子. 通过对贴附CO的络合物离子的红外光解离光谱实验获得了HC_2nO⁺正离子在1600∽3500 cm^-1范围内的红外光谱. 通过比较实验光谱和理论模拟光谱确定了HC_2nO⁺正离子具有端接氢和氧的直线型碳链衍生物结构,基态为三重态,单重态比三重基态能量高10∽15 kcal/mol. 成键分析表明HC_2nO⁺中的碳链具有连烯的结构特征.     

Cooperative Jahn-Teller ordering and magnetic structure - pyridine-N-oxide complexes of Cu2+: Cu(ONC5H5)6X2 [X = ClO−4, BF−4]1

Pyridine-N-oxide complexes CuL₆X₂ [L: C₅H₅NO ; X: BF^?₄(I), ClO^?₄(II)] with trigonal unit cells at 298 K and CuL₆²⁺ octahedra in approximately cubic primitive arrangement exhibit dynamic to static Jahn-Teller phase transitions to pseudopetragonal modifications at ≈ 90 K (I) and below 70 K (II). It found by single crystal and powder EPR-spectroscopy, that the low-temperature β-phases are characterised by a cooperative Jahn-Teller order of elongated CuO₆-octahedra, which is ferrodistortive (I) and antiferrodistortive (II) respectively. These orbital order patterns are in agreement with the symmetries of the magnetic structures found for the two complexes.     

[Co(CO2)n]+团簇的红外解离光谱实验和理论研究

本文利用红外光解离光谱研究了一价钴阳离子与二氧化碳之间的相互作用. 通过密度泛函理论计算得到[Co(CO₂)_n]⁺团簇的几何结构,并且模拟了它们的振动光谱与实验数值进行比较. 研究结果表明,在[Co(CO₂)_n]⁺(n=2∽6)团簇中,钴阳离子通过电四极矩静电作用以端点结合的方式与二氧化碳中的氧原子结合在一起. 团簇的红外光谱都集中在二氧化碳反对称伸缩的波数附近,并且随着团簇尺寸的变化出现蓝移,最后把[Co(CO₂)_n]⁺的红外光解离光谱与稀有气体贴附的[Co(CO₂)_n]⁺-Ar的红外光解离光谱进行了比较.     

Specific features of photo and thermoluminescence of Tb ions in BaO-M2O3 (M=Ga, Al, In)-P2O5 glasses

BaO-P₂O₅ glasses mixed with the three metal oxides viz., Al₂O₃, Ga₂O₃ and In₂O₃ doped with Tb₂O₃ were prepared. The glasses were characterized by X-ray diffraction and differential thermal analysis. Optical absorption and photoluminescence spectra and thermoluminescence (TL) of these glasses have been studied. From the measured intensities of various absorption bands of these glasses, the Judd-Ofelt parameters Ω₂, Ω₄ and Ω₆ have been evaluated and compared with those of other reported glass systems. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of these glasses. From this theory various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r and the emission cross-section σ^E for various emission levels of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies of all the three glasses. The analysis of TL data indicate high non-radiative losses in In₂O₃ mixed glasses.