Theoretical Study of the electronic Structure of Three Bridged Binuclear Complex Ion M_2Cl_9^<3・> : M=Cr, Mo, W

三桥双核络离子M_2Cl_9^<3・>电子结构的理论研究：M=Cr, Mo, W

• 批准号: 07640668
• 负责人: TANAKA Kiyoshi
• 金额: $ 1.47万
• 依托单位: The University of Electro-Communications
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07640668/
• 关键词: three bridged; binuclear complex ion; interaction between metal ions; CASSCF; MRSDCI; covalency; excitation energy; 電子相関; クラスター; スピン多重項; モデルポテンシャル; 配置間相互作用法; 2核遷移金属錯体; 三架橋; Cr_2Cl_9^<3->; Mo_2Cl_9^<3->; 結晶場; d-d遷移; dimer band

Three bridged complex ion, M_2Cl_9^<3・> (M=Cr, Mo) is composed of the crystal in the form of Cs_3M_2Cl_9 and M^<3+> ion is surrounded by 6 ligands in almost O_h form and two metal ions hold 3 ligans in common. Cr^<3+> and Mo^<3+> possess three d valence elctrons. The two binuclear ions show quite different electronic spectra. In the last academic year, we obtained the lowest states lead by the same configuration of the spin multiplets of 1,3,5 and 7 states separated within 13cm^<-1> for Cr case, whereas Mo ion splits the range of 8000 cm^<-1>. The calculated singlet-triplet separation of 782cm^<-1> agrees very well with observed value of 840cm^<-1>. However we could not obtain good agreement with experiment for the higher excited states. To improve the situation, we prepare 3 states averaged CASSCF MO to obtain comparable results with the ground state and carried out MRSDCI.As the interaction between metal ions is weak in Cr system, it has been expected that the electronic spectrum is interpreted well by the data of CrCl_6^<3・>. The results support the expectation ; the excited states located at 1.5-1.7eV and 2-2.5eV are interpreted as the excitation of t_2*ein one of Cr as {(ts_2^2e)^4T_2X (t_2^3)^4A_2} and {(t_2^2e)^4T_1X (t_2^3)^4A_2}, respectively. The excited states located at 1.35 and 1.4eV are expressed as {(t_2^2e)^4T_2X (t_2^3)^4A_2} and {(t_2^2e)^4T_1X (t_2^3)^4A_2}, respectively. In Mo system, covalency is much stronger than Cr case, the interpretation just as Cr is not clearly applicable but lower states are almost described as intrat_2^3 transitions in one Mo ion.

晶体以Cs_3M_2Cl_9的形式组成三桥络离子M_2Cl_9^<3·>（M=Cr，Mo），M^<3+>离子周围有6个几乎为O_h形式的配体，两个金属离子共有3个配体。Cr^<3+>和Mo^<3+>具有三价电子。这两种双核离子的电子光谱有很大的不同。在上一学年中，我们得到了Cr离子的1，3，5，7自旋多重态的最低态，这些多重态的最低态的组态是相同的，Cr离子的自旋多重态的间距在13 cm ~ 2以内<-1>，而Mo离子的自旋多重态的间距在8000 cm ~ 2以内<-1>。计算得到的单重态-三重态间距为782 cm ~ 2，<-1>与观测值840 cm ~ 2吻合得很好<-1>。然而，我们不能得到很好的协议与实验的高激发态。为了改善这种情况，我们制备了三态平均的CASSCF分子轨道，得到了与基态相当的结果，并进行了MRSDCI，由于Cr体系中金属离子间的相互作用很弱，因此我们期望用CrCl_6^&lt;3·&gt;的数据很好地解释电子光谱。结果支持了这一理论，在1.5-1.7eV和2-2.5eV处的激发态分别被解释为Cr原子中的一个原子t_2* 的激发态{（ts_2^2e）^4T_2X（t_2^3）^4A_2}和{（t_2^2e）^4T_1X（t_2^3）^4A_2}。位于1.35和1.4eV的激发态分别表示为{（t_2^2e）^4T_2X（t_2^3）^4A_2}和{（t_2^2e）^4T_1X（t_2^3）^4A_2}。在Mo体系中，共价性比Cr强得多，正如Cr那样的解释并不明显适用，但较低的态几乎被描述为一个Mo离子中的2^3内跃迁。

项目成果

E.Miyoshi, Y.Sakai K.Tanaka, M.Masamura: "Relativistic dep-Model Core Potentials for main group elements in the fourth, fifth, and sixth-row and their applications" J.Molecular Structure (THEOCHEM). (in press).

E.Miyoshi、Y.Sakai K.Tanaka、M.Masamura：“第四、第五和第六行主族元素的相对论 dep-Model 核心势及其应用”J.Molecular Structure (THEOCHEM)。

Yoshiko SAKAI Eisaku MIYOSHI: "Model Potentials for main group elements Li through Rn" J.Chem.Phys.(発表予定).

Yoshiko SAKAI Eisaku MIYOSHI：“主族元素 Li 到 Rn 的模型势”J.Chem.Phys（待提交）。

田中 皓: "On the Electronic Structure of Cu(H_2O)_2^<2+>" International J.Quantum chemistry. 64,4. 454-458 (1997)

Hiroshi Tanaka：“Cu(H_2O)_2^<2+> 的电子结构”国际量子化学 64,4（1997）。

酒井嘉子: "Model Potentials for main group elements Li Through Rn" J.Chem.Phys.106,19. 8084-8092 (1997)

Yoshiko Sakai：“主族元素 Li 至 Rn 的模型势”J.Chem.Phys.106,19 (1997)。

Kiyoshi TANAKA Helge JOHASEN: "On the electronic Structure of Cu(H_2O)_6^<2+>" Intern.J.Quantum Chem.(発表予定).

Kiyoshi TANAKA Helge JOHASEN：“论 Cu(H_2O)_6^<2+> 的电子结构” Intern.J.Quantum Chem.（待提交）。