摘要
采用 ab initio 有效核芯势(ECP)方法研究第二过渡金属双核卤化物的电子结构。首先讨论 ECP价基的准确性和可靠性,而后用其计算[M_2Cl_8]^(n-)体系(M=Mo、Tc、Ru、Rh)。结果表明:[Mo_2Cl_8]^(4-)如[Tc_2Cl_8]^(2-)的金属间存在四重键σ~2π~4δ~2,而其等电子体系[Ru_2Cl_8],[Rh_2Cl_8]^(2+),金属间键级为 0。同时还计算了[M_2X_9]^(3-)体系(M=Nb、Mo、Tc、Ru,X=Cl、Br),其电子结构表明:金属间除了 M-Cl-M 桥键联结外,还直接形成金属键。从 Nb?Ru,随原子序数增大金属键从双键变为单键,以至不成键。
The electronic structures of the second transition metals dinuclear halides were studied by ab inftio effective core potentiaf(ECP). At first, (he accuracy and reliability of ECP-based valence-electron were discussed. Then calculations on the system[M2Xg]n-(M-Mo.Tc,Ru,Rh. X = C1) have been made. The results express:ln [Mo2C18]4- and [Tc2CI8]2-.containing quadruple bouds σ2π4δ2 between metal atoms.But for Ru2Ct8 and [RhjCl8]2+ an isoelectronic system.their bond order was equal to zero.And we had calculated the [M2Xa]3- system (M = Nb,Mo,Tc.Ru, X= CI.Br).Their electronic structures show: Between metal atoms,beside M-C-M bridge boud, there were generated metal bonds directly. From Nb to Ru.lollowing the atomic number increased.the metal bonds were changed from double bond to singe and untill non-bond.
出处
《厦门大学学报（自然科学版）》
CAS
CSCD
北大核心
1990年第2期170-174,共5页
Journal of Xiamen University：Natural Science
关键词
双核卤化物
第二过渡金属
从头算
ab initio , Dinuclear halide, Pseudopotentiat, Effective core potential
