团簇NiPS_(3)异构转化热力学与动力学分析  

Thermodynamic and kinetic analysis of cluster NiPS_(3) isomerization

作　　者：宋静丽 方志刚[1] 刘立娥 魏代霞 原琳 SONG Jing-Li;FANG Zhi-Gang;LIU Li-E;WEI Dai-Xia;YUAN Lin(School of Chemical Engineering,University of Science and Technology Liaoning,Anshan 114051,China)

机构地区：[1]辽宁科技大学化学工程学院,鞍山114051

出　　处：《原子与分子物理学报》2024年第4期83-90,共8页Journal of Atomic and Molecular Physics

基　　金：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(202110146027,20201014600,202010146016);辽宁省大学生创新创业训练计划项目(202110146049,202110146052,202110146030,202110146055,202110146040,202110146056)。

摘　　要：为了探究团簇NiPS_(3)的稳定性和异构转化机理,本文利用密度泛函理论,在B3LYP/def2-tzvp的量化水平下,对团簇NiPS_(3)的初始构型进行优化分析和异构化计算,得到了10种优化构型和7种异构转化类型.从化学反应的热力学和动力学对异构转化反应进行讨论分析,得出了以下结论:团簇NiPS_(3)的异构转化反应依赖于非金属-金属和非金属-非金属之间的成键与断键;反应物与产物稳定性差别越大,反应进行的越彻底;除反应2((2))→1((4))外,其他的异构化反应在低温下更加易于自发进行;异构化反应趋向于正向进行,即能量高的构型向能量低的构型转换更容易;构型1((2))、构型2((2))和构型1((4))是团簇NiPS_(3)异构转化的最终产物,进行相关材料的研究、开发和生产时,可优先考虑.In order to explore the stability of cluster NiPS_(3) and the mechanism of isomerization transformation,in this paper,density functional theory was used to optimize the initial configuration of cluster NiPS_(3) and calculate the isomerization under the quantum chemistry calculation level of B3LYP/def2-tzvp.Ten optimal configurations and seven isomerization transformation types were obtained.Based on the thermodynamics and kinetics of chemical reactions,the following conclusions are drawn:the isomerization transformation of cluster NiPS_(3) depends on the bonding and bonded breaking between non-metal and non-metal.The greater the difference between the stability of reactants and products,the more thorough the reaction.Except reaction 2~((2))→1~((4)),other isomerization reactions are more spontaneous at low temperature.The isomerization reaction tends to proceed in the forward direction,that is to say,the higher energy configuration is easier to convert to the lower energy configuration.Configurational 1~((2)),configurational 2~((2))and configurational 1~((4))are the final products of cluster NiPS_3 isomerization,and could be given priority in the research,development and production of related materials.

关 键 词：团簇NiPS_(3) 密度泛函理论 异构转化 过渡态理论 范特霍夫方程 

分 类 号：O641.12[理学—物理化学]