路艳罗
,
卫敏
,
杨文胜
,
D.G.Evans
,
段雪
应用化学
doi:10.3969/j.issn.1000-0518.2002.11.005
由高温焙烧法制备层状前驱体Nax[Li1/6Mn5/6]O2,再经离子交换反应得到O2结构层状产物Liy[Li1/6Mn5/6]O2. 采用离子交换和元素分析推测前驱体中Li+位于层板上. XRD测试结果表明,Liy[Li1/6Mn5/6]O2属六方晶系,P3ml空间群;激光粒度分析仪测定Na0.06Li0.65[Li0.10Mn0.88]O2的最可几粒径为2.88 μm;BET法测定其比表面积为4.68 m2/g;TEM显示其形貌为存在缺陷的层状六方结构. XRD和元素分析结果表明,反应物n(Na)/n(Mn)比直接影响着前驱体及最终产物的晶体结构和化学组成.
关键词:
Liy[Li1/6Mn5/6]O2
,
层状材料
,
晶体结构
,
化学组成
任玲玲
,
何静
,
马润宇
,
段雪
,
D.G.Evans
应用化学
doi:10.3969/j.issn.1000-0518.2001.11.001
通过X射线粉末衍射和透射电镜研究了在青霉素酰化酶(PGA)作用下双金属复合氧化物(LDO)记忆效应与其组成(层板电荷密度、层板离子种类)的关系.结果表明,500℃焙烧水滑石得到的LDO,其结构由前体的有序层状结构成为层板的无序堆积.随层板碱性降低,酶对LDO作用明显,LDO保持其无序层板堆积;随层板碱性增加,酶对LDO作用减小,LDO的记忆效应明显,趋于由无序堆积层板向有序层状结构转变.
关键词:
双金属复合氧化物
,
水滑石
,
记忆效应
,
青霉素酰化酶
,
固定化酶
Physica B-Condensed Matter
Similar to the cases of 3d(n) ions in 4-fold (or 8-fold) and 6-fold cubic coordinations, a simple and uniform method that calculates the spin-lattice coupling coefficients G11 and G44 for those ions in the more complex 12-fold cubic coordination from the derivatives of zero-field splittings in low symmetries with respect to the distinct structural parameters has been established. Through this method, the analytic expressions of G11 and G44 for 3d5 ions in this cubic coordination based on various mechanisms and models have been given. The results are rather different from those in 4-fold (or 8-fold) and 6-fold cubic coordinations. As an example, the coefficients G11 and G44 for Fe3+ in K+ site ( 12-fold cubic coordination) as well as Ta5+ site (6-fold cubic coordination) of KTaO3 crystal are studied from the important spin-orbit coupling mechanism. When we compare these results with the experimental findings, it appears that the Fe3+ ion is in a Ta5+ site, and not in a K+ site as shown by some researchers.
关键词:
s-6-state ions;symmetry;formulas
Communications in Theoretical Physics
By successively taking into account various interactions for d(2) ions in trigonally distorted cubic crystal fields, detailed analyses, derivations and calculations of the zero-field splitting (ZFS) and g factors of the ground state have been carried out; and their physical essentials and origins have been clearly revealed. The mistakes and shortcomings in some references have been corrected and improved. The calculated results are in excellent agreement with experimental data and much better than those of previous work. It is found that both the combined action of the trigonal field and spin-orbit interaction and the interaction between the ground state and excited states are quite necessary for causing ZFS of the ground state, and both the spin-orbit interaction and the admixture between the ground state and excited states are necessary for causing the deviation of g factors of the ground state from spin-only values.
关键词:
zero-field splitting;g factors;d(2) ions;crystal field;combined;action;admixture of wavefunction
Journal of Physics and Chemistry of Solids
The g-shifts Ag( = g-g(s), where g(s) approximate to 2.0023 is the free-ion value) of the isoelectronic 3d(3) series Cr3+. Mn4+ and Fe5+ in SrTiO3 crystals are calculated from the high-order perturbation formula based on the cluster approach for 3d3 ion in cubic octahedral site. The formula includes not only the contribution from the crystal-field (CF) mechanism, but also that from the charge-transfer (CT) mechanism (which is omitted in the CF theory). From the calculations, it is found that the contribution Delta g(CT) from the CT mechanism in sign is contrary to the corresponding Delta g(CF) from the CF mechanism and the relative importance of CT mechanism (characterized by vertical bar Delta g(CT)/Delta g(CF)vertical bar) increases with the increasing valence state (and hence the atomic number) of 3d(3) ion. The positive g-shift Delta g of SrTiO3:Fe5+ is due mainly to the contribution of CT mechanism. So, for the explanations of g factors of the high valence state 3d" ions (e.g. Mn4+ and Fe5+) in crystals, the contributions from both CF and CT mechanisms should be taken into account. (c) 2005 Elsevier Ltd. All rights reserved.
关键词:
oxides;crystal fields;electronic paramagnetic resonance;optical;properties;electron-paramagnetic-resonance;atomic screening constants;scf;functions;luminescence;parameters;spectra;temperature;manganese;lattices;csmgbr3
Physica B-Condensed Matter
The perturbation formula of g factor for 3d(7) ion in cubic octahedral crystals has been obtained from a cluster approach. In the formula, the parameters related to the configuration interaction and the covalency reduction effect can be obtained from the optical spectra of the crystal under study and so no adjustable parameters are applied. From the formula, the g factors for Co2+ in fluoroperovskites LiBaF3, KMBF3, KZnF3 and CsCdF3 are calculated. The calculated results are in agreement with the observed values. The g factor following the order of LiBaF3 : Co2+ < KMgF3 : Co2+ < KZnF3: Co2+ < CsCdF3 : Co2+ is also explained. (C) 2000 Elsevier Science B.V. All rights reserved.
关键词:
electron paramagnetic resonance;crystal- and ligand-field theory;Co2+;LiBaF3;KMgF3;KZnF3;CsCdF3;perovskite;transition;impurities;crystals
