团簇FePS3的电子性质及反应活性密度泛函研究
Density functional study on the electronic properties and reactivity of the FePS3 cluster
魏代霞 1方志刚 1吴庭慧 1宋静丽 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, 鞍山 114051
- 折叠
摘要
以团簇FePS3为局域模型,在B3LYP/def2-tzvp水平下采用Gaussian 09程序对团簇FePS3进行结构优化及虚频验证,获得12种稳态构型,分析了这12种构型的原子电荷量、电子自旋密度及反应活性.结果表明:团簇FePS3中S原子为电子受体,Fe、P原子为电子供体,Fe比P原子更容易失去电子,团簇FePS3整体的电子流向为从Fe、P原子流入S原子;Fe、P原子间和Fe、S原子间的过剩电子主要为自旋向下的β成单电子,P、S原子间和S、S原子间的过剩电子主要为自旋向上的α成单电子;构型4(4)、2(2)、1(2)、2(4)、1(4)和4(2)的电子自旋密度的对称性最好,稳定性最高,因此这6种构型可能为团簇FePS3的优势构型;构型6(2)的前线轨道(HOMO-LUMO)能隙差最小,最容易发生电子跃迁,反应活性最高;构型2(4)的HOMO-LUMO轨道能隙差最大,反应活性最低.
Abstract
Using the cluster FePS3 as the local model, structure optimization and imaginary frequency verification were carried out using the Gaussian 09 program at the B3LYP/def2-tzvp level, and 12 steady-state configurations were obtained. The atomic charges, electron spin densities and reactivities of these 12 configurations were ana-lyzed. The results show that the S atom in the FePS3 cluster is an electron acceptor, and the Fe and P atoms are e-lectron donors. Fe atoms are more likely to lose electrons than P atoms. The overall direction of electron flow in the FePS3 cluster is from Fe and P to S atoms. The excess electrons between Fe and P atoms and between Fe and S at-oms are mainly spin-down β-single electrons, and the excess electrons between P and S atoms and between S and S atoms are mainly spin-up α-single electrons. The electron spin densities of configurations 4(4) , 2(2) , 1(2) , 2(4) , 1(4) and 4(2) have the best symmetry and the highest stability. Hence these six configurations may be the dominant configurations of the FePS3 cluster. The frontier orbital ( HOMO-LUMO) energy gap of configuration 6(2) is the smallest, which is, therefore, most prone to electron transitions and has the highest reactivity. The HOMO-LUMO orbital energy gap of configuration 2(4) is the largest and this configuration has the lowest reactivity.
关键词
团簇FePS3/密度泛函理论/电荷量/自旋密度/反应活性Key words
FePS3 cluster/density functional theory/quantity of electric charge/spin density/reactivity引用本文复制引用
基金项目
国家自然科学基金重点项目(51634004)
国家级大学生创新创业训练计划项目(202310146026/202310146027/202310146025)
辽宁省大学生创新创业训练计划项目(S202310146046)
出版年
2024
NETL
NSTL
万方数据