Bonding and Mssbauer Isomer Shifts in(Tl,Pb)-1223 Cuprate

By using the chemical bond theory of dielectric description, the chemical bond parameters of (Tl, Pb) - 1223 was calculated. The results show that the Sr-O, Tl-O, and Ca-O types of bond have higher ionic character and the Cu-O types of bond have more covalent character. Mssbauer isomer shifts of 57Fe and 119Sn doped in (Tl, Pb) -1223 were calculated by using the chemical environmental factor, he, defined by covalency and electronic polarizability. Four valence state tin and three valence iron sites were identified in 57Fe, and 119Sn doped (Tl, Pb) -1223 superconductor. We conclude that all of the Fe atoms substitute the Cu at square planar Cu (1) site, whereas Sn prefers to substitute the square pyramidal Cu (2) site.

Bonding and Mssbauer Isomer Shifts in (Hg, Pb)-1223 Cuprate

By using the chemical bond theory of dielectric description, the chemical bond parameters of (Hg, Pb) 1223 were calculated. The results show that the (Ba, Sr) O and Ca-O types of bond have higher ionic character, while the Cu-O and (Hg, Pb) O types of bond have more covalent character. Mssbauer isomer shifts of 57 Fe and 119 Sn doped in (Hg, Pb) 1223 were calculated by using the chemical environmental factor, h e, defined by covalency and electronic polarizability. Four valence state tin and three valence iron sites were identified in 57 Fe and 119 Sn doped (Hg, Pb) 1223 superconductor. It can be concluded that all of the Fe atoms substitute the Cu at square planar Cu(1) site, whereas Sn prefers to substitute the square pyramidal Cu(2) site.

X@(HAINH)_(12)和X(HAINH)_(12)(X=F^-,Cl^-,Br^-,O^(2-),S^(2-),Se^(2-))复合物的结构和稳定性

用DFT的B3LYP方法在6-31G(d)基组的水平上,对闭式多面体簇合物(HA1NH)12及其内含式X@(HA1NH)12外接式X(HA1NH)12(X=F-,Cl-,Br-,O2-,S2-,Se2-)复合物的结构进行了构型优化和能量计算,并讨论了几何构型、自然键轨道(NBO)、振动频率、能量参数及NMR数据与结构的关系,最后得到复合物结构的稳定性信息,具有Th对称性的X@(HA1NH)12(X=F-,Cl-,Br-,S2-,Se2-)复合物和具有C3对称性的O2-@(HA1NH)12复合物为内含式的基态结构,从能量角度分析,内含式复合物比外接式复合物的结构稳定.

Influence of Ti^(4+) doping on hyperfine field parameters of Mg_(0.95)Mn_(0.05)Fe_(2-2x)Ti_(2x)O_4(0≤x≤0.7)

The mixed spinel ferrite system Mg0.95Mn0.05Fe2-2xTi2xO4(0≤x≤0.7) was synthesized by the conventional solid-state reaction technique.The effect of Ti4+ doping was studied by using the Mssbauer spectroscopy measurements at room temperature.From the analysis of the Mssbauer spectra,it is observed that s-electron density,electric field gradient(EFG),quadrupole coupling constant(QCC) and the net hyperfine magnetic fields acting on the M-ssbauer nuclei-FeA3+ and FeB3+ change with the increase of Ti4+ doping in Mg0.95Mn0.05Fe2O4.The hyperfine magnetic field decreases with the increase of Ti4+ doping.

Mssbauer spectra of MnFe_(2-2x)Al_(2x)O_4(0≤x≤0.4) ferrites

The effect of non-magnetic Al3+ ion doping on the magnetic properties of MnFe2-2xAl2xO4(0≤x≤0.4) spinel ferrites was studied using Mssbauer spectroscopy measurements at room temperature.From the Mssbauer study,it is observed that the resolved hyperfine sextets are due to the distribution of Fe ions on the two sublattices of the spinel ferrites.The value of the isomer shift obtained from the fitting of the Mssbauer spectra indicates that Fe ions are in +3 state.A paramagnetic doublet is observed at degree of inversion x=0.4,superimposed on the hyperfine sextets,indicating that the super-exchange interaction A-B decreases due to the dilution of sublattice by Al3+ ions.The hyperfine magnetic field decreases at both interstitial sites of tetrahedral(A) and octahedral(B) with the increase in Al concentration.

杂苯C_5H_5X(X=N,P,As,Sb,Bi)芳香性的核独立化学位移(NICS)与异构体稳定化能(ISE)研究

应用量子化学方法,通过核独立化学位移(NICS)和异构体稳定化能(ISE)的计算,研究了苯及第五主族元素取代杂苯分子C5H5X(X=N,P,As,Sb,Bi)的芳香性与稳定性.局域轨道定位函数局部最大值的计算结果表明,分子中C—X成键强度与实验稳定性顺序一致.从头算与密度泛函理论对分子的化学位移计算结果各异,计算值与实验值相关分析表明,Hartree-Fock方法对所研究体系的NICS比密度泛函理论具有更好的相关性.在分子环平面上方0.8～0.9处的NICS是芳香性判据的最佳选择,由自然定域分子轨道分解NICS最大处的zz张量值,结果显示π键对分子的芳香性起主要贡献.异构体稳定化能与NICS(max)的zz张量及π键(NICS(max)zzπ)均有很好的相关性,可以表征杂苯分子C5H5X全局芳香性,其顺序为:苯>吡啶>磷杂苯>砷杂苯>锑杂苯>铋杂苯.特别地,对这类分子π轨道的研究发现不包含X原子的π轨道将产生异常大的π键芳香性,这一现象可为分子磁性设计提供理论指导.