Study of multinuclear f-electronic structures by a multidimensional non-linear optimization method

多维非线性优化方法研究多核f电子结构

基本信息

批准号：
15550046
负责人：
ISHIKAWA Naoto
金额：
$ 2.3万
依托单位：
Chuo University (2005)Tokyo Institute of Technology (2003-2004)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

项目摘要

The computational method which Ishikawa previously proposed for determination of sublevel structure of ground multiplets of isostructural series of lanthanide complexes was applied to several representative classes of lanthanide complexes. The new information about electronic structures of the 4f-complexes led to new physico-chemical aspects of lanthanide complexes as follows.(1)Ligand field parameters and ground multiplet structures have been determined for bis(phthalocyaninato)lanthanides Pc_2Ln^- and tris(dipicolinato)lanthanides Ln(dipic)_3^<3->. Temperature dependence of magnetic susceptibilities and NMR data of these complexes were quantitatively elucidated based on the quantum-chemical view for the first time.(2)Ligand field parameters of the tris(phthalocyaninato) dinulear lanthanide complexes Pc_3Ln_2 were determined. This led to the elucidation of the nature of the f-f interaction between the two lanthanide ions in the complexes.(3)SMM behavior of single-ionic lanthanide comp … More lex was discovered for Pc_2Tb^- and Pc_2Dy^-.(4)The π-radical Pc_2Tb^0 showed SMM behavior at even higher temperature range by 10K than the anionic complex. In the π-radical SMM, two spin system, S_z=(+1/2,-1/2) and J_z=(+6,-6) are present in a single molecule, leading to the pi-f interaction that yields this remarkable effect.(5)The contribution of the f-f interaction to the dynamical magnetism of the dinuclear terbium complexes Pc_3Tb_2 was elucidated both experimentally and theoretically.(6)Magnetic susceptibility measurements in the sub-kelvin range revealed that Pc_2Tb^-, Pc_2Dy^- and Pc_2Ho^- exhibit staircase-like structures in magnetization hysteresis curves. These structures are caused by the quantum-tunneling of magnetization (QTM).(7)Ln(dipic)_3^<3-> with odd numbers of 4f-elections exhibited significant dc-magnetic field dependences of ac susceptibilities. While none of the six heavy-lanthanide complexes showed magnetization lag from ac magnetic field of 10 - 10^3 Hz above 1.7K, the Dy, Er and Yb complexes with odd numbers of 4f-electrons exhibited the magnetization lag in a dc field. Less

Ishikawa先前提出的用于确定兰烷基复合物的地面倍数的巨型结构的计算方法应用于兰烷基复合物的几种代表性类别。 The new information about electronic structures of the 4f-complexes led to new physical-chemical aspects of lanthanide complexes as follows.(1)Ligand field parameters and ground multiplet structures have been determined for bis(phthalocyaninato)lanthanides Pc_2Ln^- and tris(dipicolinato)lanthanides Ln(dipicolinato)_3^<3->.基于量子化学观点，对这些复合物的磁敏感性和NMR数据的温度依赖性首次定量阐明。（2）确定Tris（苯烷酸）diluar lanthanide conffffers PC_3LN_2的Tris（苯甲酸）diluar Lanthanide配合物的配体场参数。这导致阐明了复合物中的两个灯笼离子之间F-F相互作用的性质。（3）单离世兰烷基comp的SMM行为……在PC_2TB^ - 和PC_2DY^ - 。（4）π-Radical PC_2TB^0的PC_2TB^ - 。（4）在更高温度范围内显示了SMM的PC_2TY^ - 。（4）。在π-Radical SMM中，两个分子中存在两个自旋系统，S_z =（+1/2，-1/2）和J_z =（+6，-6）存在于单个分子中，从而导致PI-F相互作用，从而产生这种显着效果。（5）F-F相互作用对f-F相互作用的贡献对DiNucleciles teruclecle teruciled teruciles pc_3ttbim pc_3TTTTTTTTTTTTTTTTTTTTTTTTT，理论。（6）子kelvin范围内的磁敏感性测量结果表明，PC_2TB^ - ，PC_2DY^ - 和PC_2HO^ - 在磁化滞后曲线中暴露的类似楼梯的结构。这些结构是由磁化（QTM）的量子隧道引起的。（7）Ln（Dipic）_3^<3-> 4F电子的奇数暴露于AC敏感性的显着DC磁场依赖性。虽然六个重型灯泡复合物中没有一个在1.7k上方的10-10^3 Hz的AC磁场中显示出磁化滞后，但Dy，ER和YB复合物具有4F电子的奇数，在DC场中暴露了磁化强度滞后。较少的