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~...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。展开更多
Structure of 19 cluster cations for AgPn+ and AumPn+ generated by laser plasma reactions have been designed according to chemical bond and calculated using DV-Xamethod of quantum chemistry. The results show that P ato...Structure of 19 cluster cations for AgPn+ and AumPn+ generated by laser plasma reactions have been designed according to chemical bond and calculated using DV-Xamethod of quantum chemistry. The results show that P atoms always tend to form P4fragInnt, then combine with Au atoms. The ability of Au atoms to form cluster is stronger than Ag atorns. It combines with P4 fragment after forming chain or cluster of Au atoms.In many-nuclear system the 5d2, 6s1 hybrid orbitals of Au atoms overlap to foTm cluster skeleton orbitals with each other, there axe a lot of metallic nonbonding orbitals.展开更多
文摘采用 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。
文摘Structure of 19 cluster cations for AgPn+ and AumPn+ generated by laser plasma reactions have been designed according to chemical bond and calculated using DV-Xamethod of quantum chemistry. The results show that P atoms always tend to form P4fragInnt, then combine with Au atoms. The ability of Au atoms to form cluster is stronger than Ag atorns. It combines with P4 fragment after forming chain or cluster of Au atoms.In many-nuclear system the 5d2, 6s1 hybrid orbitals of Au atoms overlap to foTm cluster skeleton orbitals with each other, there axe a lot of metallic nonbonding orbitals.
