Fe_(x)Cu_(y)(x+y=2)羰基簇合物前线轨道特征及其反应活性的理论研究  

Theoretical Study of Frontier Orbital Properties and Reactive Activity of Fe_(x)Cu_(y)(x+y=2) Carbonyl Complexes

作　　者：刘晓荣 慕红梅 LIU Xiaorong;MU Hongmei(College of Environment and Chemical Engineering,Lanzhou Resources&Environment Voc-Tech University,Lanzhou 730021,China)

机构地区：[1]兰州资源环境技术大学环境与化工学院,甘肃兰州730021

出　　处：《河南科技》2022年第20期70-73,共4页Henan Science and Technology

摘　　要：本研究采用密度泛函理论,计算研究了Fe_(x)Cu_(y)(x+y=2)羰基簇合物的结构、吸附能和前沿分子轨道特征,分析了第二金属原子在配体反应中的作用,也证实了CO与双金属团簇的反应比纯团簇体系的反应更容易,其中Fe_(x)Cu_(y)具有最大的分步吸附能。最后利用HOMO和LUMO的能级差来考察第二金属对羰基配合物的反应活性的影响,发现双金属团簇羰基配合物比相应的Fe_(2)和Cu_(2)能量低,其中FeCu(CO)_(2)比其他双金属羰基配合物具有更低的能隙和相对高的吸附能。这表明在反应中调节双金属团簇以获得更高活性的羰基配合物是可行的。In this study,the adsorption of CO on Fe_(x)Cu_(y)(x+y=2) clusters were studied by BPW91method,all conceivable geometries,adsorption energy and frontier molecular orbitals of carbonyl complexes were explored.The results show that bimetallic clusters tend to have higher stepwise CO adsorption energy than corresponding pure clusters,and the adsorption capacity of FeCu with CO is substantially larger than that of other carbonyl complexes.Moreover,the frontier molecular orbital theory was used to analyze the effect of the second element in the ligand reactions,which also confirmed that the reactions of CO with bimetallic clusters are easier than that of pure cluster systems.Finally,the energy gaps of HOMO and LUMO were used to explore the reactive activity of carbonyl complexes,it was found that the bimetallic clusters are lower than that of the Fe_(2) or Cu_(2) ,and the FeCu(CO)_(2) has lower energy gap than that of other carbonyl complexes.This suggests that it may be possible to tune bimetallic cluster to get higher activity carbonyl complexes in the reactions.

关 键 词：Fe_(x)Cu_(y)(x+y=2) 羰基配合物 密度泛函理论 反应活性 

分 类 号：O643.12[理学—物理化学]