Competition between(18,18)and(18,16)Configurations in Ni2(CO)5:An Isomerization Energy Decomposition Analysis  

异构化能量分解分析Ni_(2)CO_(5)的(18,18)与(18,16)构型竞争

作　　者：Zhi-ling Liu Yan Bai Ya Li Jing He Qing-yang Lin Fu-qiang Zhang Hai-shun Wu Jian-feng Jia 刘志凌;白燕;李雅;何静;林青杨;张富强;武海顺;贾建峰(山西师范大学化学与材料科学学院,磁性分子与磁信息材料教育部重点实验室,临汾041004)

机构地区：[1]School of Chemical and Material Science,Key Laboratory of Magnetic Molecules&Magnetic Informa-tion Materials,Ministry of Education,Shanxi Normal University,Linfen 041004,China

出　　处：《Chinese Journal of Chemical Physics》2021年第3期287-296,I0026-I0038,I0047,共24页化学物理学报（英文）

基　　金：supported by the National Natural Science Foundation of China(No.21571119 and No.21603130);the Shanxi Province Science Foundation for Youths(No.201901D211395);the 1331 Engineering of Shanxi Province;the Start-up fund from Shanxi Normal University。

摘　　要：The potential energy landscape of the neutral Ni_(2)(CO)_(5) complex was re-examined.A new C_(2v) structure with double bridging carbonyls is found to compete with the previously proposed triply carbonyl-bridged D_(3h) isomer for the global minimum of Ni_(2)(CO)_(5).Despite that the tri-bridged isomer possesses the more favored(18,18)configuration,where both metal centers satisfy the 18-electron rule,the neutral Ni_(2)(CO)_(5) complex prefers the di-bridged geometry with(18,16)configuration.The isomerization energy decomposition analysis reveals that the structural preference is a consequence of the maximization of electrostatic and orbital interactions.

关 键 词：Nickel carbonyl Density functional theory 18-electron rule Isomerization energy decomposition analysis Three-center two-electron 

分 类 号：O641.4[理学—物理化学]