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

三个桥接复合体， M_2Cl_9^<3·> （M=Cr， Mo）由Cs_3M_2Cl_9和M^<3+>离子组成的晶体由O_h形式中的6根和2根金属共持有3根。Cr^<3+> and Mo^<3+> possess three d valence elctrons。这是两个双核装置，展示了一个非常不同的电子装置。在过去的学术年中，我们获得了最低的国家，在13厘米之间分离的1、3、5和7个国家的相同配置中，Cr案件中的Mo离子碎片的范围为8000厘米^<-1>。calculated singlet-trilet separation of 782 cm ^\-1> agrees very well with observed value of 840 cm ^\-1>。我们无法达成一项与更高兴奋的国家的实验达成好的协议。为了改善情况，我们准备3个国家平均CASSSCF MO可以获得与地面状态相比较的结果，并获得MRSDCI。由于金属在Cr系统中的相互作用很弱，它被预期到电子光谱被CrCl_6^<3>的数据解释良好。结果支持期望;在1.5- 1.7 eV和2- 2.5 eV被解释为t_2 *ein one of Cr {（ts_2^2 e）^4 T_2 X（t_2^3）^4 A_2}和{（t_2^2 e）^4 T_1 X（t_2 ^3）^4 A_2}，响应。The excited states located at 1.35 and 1.4 eV are expressed as {（t_2^2 e）^4 T_2 X（t_2^3）^4 A_2} and {（t_2^2 e）^4 T_1 X（t_2^3）^4 A_2}， respectively。在Mo系统中，覆盖性比Cr情况更强，解释只是Cr不明显适用，但较低的国家几乎被描述为一个Mo ion中的2 ^3转换。

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.