摘要
采用ABCluster软件对实验发现的AuFe(CO)_(5)^(-)物种所有可能几何进行搜索,随后对其最低能量结构在B3LYP/Lanl2DZ对Fe和Au,6-311++G(d,p)对C和O水平下进行了全参数优化和振动分析,从而获得其结构参数和振动频率。理论计算表明,AuFe(CO)_(5)^(-)的最低能量为C_(1)对称性,有较大的HOMO与LUMO能级差预示其较高的稳定性。AuFe(CO)_(5)^(-)校正后的振动光谱与实验测量的振动光谱吻合较好,表明计算获得的结构合理。成键性质分析表明,该簇合物是典型的金属羰基配离子,具有典型的σ-π授受键,配位后C-O伸缩振动频率从自由态的2143 cm^(-1)降低到1896~2040 cm^(-1)。
ABCluster searched all possible geometries of AuFe(CO)_(5)^(-)species,and their lowest energy structures were followed by full parameter optimization and vibration analysis at C and O levels in B3LYP/Lanl2DZ pairs Fe and Au,6-311++G(d,p)to obtain their structural parameters and vibration frequencies.Theoretical calculations show that the lowest energy of AuFe(CO)_(5)^(-)is C_(1) symmetry,and its larger energy level difference between HOMO and LUMO indicates its higher stability.The corrected vibrational spectrum of AuFe(CO)_(5)^(-)is in good agreement with the experimentally measured vibrational spectrum,indicating that the calculated structure is reasonable.Analysis of bonding properties shows that AuFe(CO)_(5)^(-)is a typical metal carbonyl ligands,with typicalσ-πbonding.After coordination,C-O stretching vibration frequency decreases from 2143 cm^(-1) in free state to(1896~2040 cm^(-1)).
作者
耿琳
叶藤
刘斌
王志银
许琼
黄文登
Geng Lin;Ye Teng;Liu Bin;Wang Zhiyin;Xu Qiong;Huang Wendeng(Shaanxi Key Laboratory of Catalysis,College of Chemical&Environment Science,Shaanxi University of Technology,Hanzhong 723000,China)
出处
《山东化工》
CAS
2022年第20期61-64,共4页
Shandong Chemical Industry
基金
陕西省自然科学基金项目(2019JM-213)。
关键词
羰基铁金簇合物
密度泛函理论
几何构型
振动光谱
成键特性
能级差
carbonyl iron gold cluster
density functional theory
geometric configuration
vibrational spectrum
energy level
bonding characteristic
作者简介
耿琳,女,研究生在读,研究方向:理论与计算化学;通信作者:许琼,女,教授,研究方向:理论与计算化学,硼化学。
