团簇FePS3的极化率及催化性质研究
The Study on the Polarizability and Catalytic Properties of FePS3 Clusters
魏代霞 1方志刚 1宋静丽 1吴庭慧 1刘立娥 1原琳1
作者信息
- 1. 辽宁科技大学化学工程学院,辽宁 鞍山 114051
- 折叠
摘要
为探究团簇FePS3 各优化构型内部电子在受外电场影响时的变化情况及其催化性质,运用密度泛函理论的B3LYP杂化泛函方法,并使用def2-tzvp基组对设计出的几何构型进行全参数优化和频率计算,共得到在二、四重态下的 12 种优化构型.从各构型的极化率、能隙差、态密度图、HOMO和LUMO轨道图以及反应活性参数分析发现:构型 1(2)的极化率和极化率各向异性不变量均最大,易受外电场影响且容易发生形变.构型 4(4)和 2(2)对外电场响应能力较弱且结构最紧凑,不易发生形变.构型 6(2)的能隙差最小,电子跃迁最容易,并且该构型的第 1 电离能相对较小,电子亲和能、电负性和亲电指数均相对较大,催化活性最强.分析比较态密度图和HOMO、LUMO轨道图发现:团簇FePS3 的失电子能力强于其得电子能力,且S原子对团簇HOMO轨道和LUMO轨道的贡献大于P、Fe原子,这表明团簇FePS3 的催化活性主要由S原子贡献,但是P、Fe原子的贡献作用亦不可忽视.
Abstract
In order to explore the change of internal electrons in each optimal configuration of FePS3 cluster under the influence of external electric field and its catalytic properties,the B3LYP hybrid functional method in density functional theory is used to optimize the designed geometries by using def2-tzvp basis set for full parameter optimiza-tion and frequency calculation,and a total of 12 optimal configurations in two and four states are obtained.From the analysis of the polarizability,energy gap difference,state density diagram,HOMO and LUMO orbital diagram and re-action activity parameters of each configuration,it is found that configuration 1(2)has the largest polarizability and anisotropy invariants,and is easily affected by external fields and deformation.Configurations 4(4)and 2(2)have weak response to external fields and are the most compact structures,which are not susceptible to deformation.Con-figuration 6(2)has the smallest energy gap difference and the easiest electron transition,and the first ionization ener-gy is relatively small,the electron affinity,electronegativity and electrophilic index are relatively large,and the cata-lytic activity is the strongest.It is found that the electron loss ability of FePS3 cluster is stronger than the electron gain ability,and the contribution of S atom to the HOMO and LUMO orbitals of the cluster is greater than that of P and Fe atoms,indicating that the catalytic activity of FePS3 cluster is mainly contributed by S atom,and the contri-bution of P and Fe atoms cannot be ignored.
关键词
团簇FePS3/密度泛函理论/极化率/能隙差/反应活性Key words
cluster FePS3/density functional theory/polarizability/energy gap difference/reactivity引用本文复制引用
基金项目
国家自然科学基金(51634004)
国家级大学生创新创业训练计划(202310146026)
国家级大学生创新创业训练计划(202310146027)
国家级大学生创新创业训练计划(202310146025)
辽宁省大学生创新创业训练计划(S202310146046)
出版年
2024
NETL
NSTL
万方数据