摘要
为了从理论层面深入探究团簇Co_(n)MoS(n=1~5)的电子性质、光学性质及磁性,弄清其内在关联,依据拓扑学原理和密度泛函理论,在B3LYP/def2-TZVP量子化学水平和多个自旋多重度下对该团簇进行结构优化并分析。结果表明:团簇Co_(n)MoS共有21种稳定构型;通过对NPA(自然布居分析,natural population analysis)电荷、静电势、亲电指数、电离势、光学电负性和折射率等分析得出,金属原子有高概率失去电子,非金属原子相对更容易得到电子,团簇Co_(5)MoS中的构型5a在最稳定构型中有高的得失电子能力、反应活性和折射率,Co和Mo原子易发生亲核反应,S原子易发生亲电反应;对该团簇自旋布居数、原子磁矩、轨道磁矩和态密度分析发现,该团簇磁性主要由Co原子的d轨道提供,且团簇Co_(3)MoS表现出了比其它尺寸团簇更为稳定和优异的磁性。最终得出团簇Co_(3)MoS在磁性方面有较好的表现且构型5a在活性和光学领域有一定的潜力。
To investigate the electronic,optical,and magnetic properties of the cluster Co_(n)MoS(n=1-5)at the theoretical level and to clarify its inherent relevance,the structure of the cluster was optimized and analyzed at the B3LYP/def2-TZVP quantum chemical level and multiple spin multiplexes based on topological principles and density functional theory.The results show that there are 21 stable configurations of the cluster Co_(n)MoS,which mostly exist in stereo form,and the conformation na is the most stable and the overall cluster stability tends to be more stable as the cluster size increases;the analysis of NPA(natural population analysis)charge,electrostatic potential,electrophilic index,ionization potential,optical electronegativity,and refractive index,etc.shows that metal atoms have a high probability of losing electrons and non-metal atoms are relatively more likely to gain electrons;the configuration 5a in the cluster Co_(5)MoS has high electron gain and loss ability,reactivity,and refractive index in the most stable configuration,but it is the least chemically stable;Co and Mo atoms are prone to nucleophilic reactions and S atoms are prone to electrophilic reactions,and the active site is predicted provisionally from the electrostatic potential extreme site;the analysis of the spin population,atomic magnetic moments,orbital magnetic moments,and density of states of the cluster reveals that the magnetic properties of the cluster are mainly provided by the d orbital of the Co atom,the non-metallic atom S contributes less to the magnetic properties and the orbital hybridisation has an effect on the magnetic properties to some extent,the cluster Co_(3)MoS exhibits more stable and excellent magnetic properties than other size clusters.It is concluded that the cluster Co_(3)MoS has a good performance in magnetic properties and configuration 5a has some potential in the field of activity and optics.
作者
王智瑶
方志刚
王洁
毛智龙
曾鑫渔
吴庭慧
宋嘉
WANG Zhi-Yao;FANG Zhi-Gang;WANG Jie;MAO Zhi-Long;ZENG Xin-Yu;WU Ting-Hui;SONG Jia(School of Chemical Engineering,University of Science and Technology Liaoning,Anshan,Liaoning 114051,China)
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
2022年第8期1512-1522,共11页
Chinese Journal of Inorganic Chemistry
基金
国家自然科学基金重点项目(No.51634004)
国家级大学生创新创业训练计划(No.202110146027,202010146009,202010146016)资助。
