摘要
为了进一步完善团簇Co_(3)MoS的理论研究,同时也为研究团簇Co_(3)MoS异构化转化机理,依据密度泛函理论和过渡态理论,采用量子化学软件运行及以B3LYP/Lanl2dz水平为初始条件,运用热力学和化学动力学方法对该团簇进行了分析,并对相关异构化反应进行了预测。结果表明:团簇Co_(3)MoS各异构化反应以正反应方向为主,TS^(3(2)→1(4))异构化反应最易发生转化,TS^(2(4)→1(2))转化难度最大,构型1^((4))、1^((2))、2^((4))、2^((2))、3^((4))、3^((2))均可稳定存在;异构化反应3^((2))→1^((4))转化得最为彻底,反应限度比其他异构化过程大,2^((4))→1^((2))转化过程中消耗的活化能最多且转化最不彻底;平衡常数与反应物、生成物热力学稳定性存在联系;能量差与平衡常数的函数方程、范特荷夫方程的积分形式、吉布斯函数可以对团簇Co_(3)MoS异构化反应进行预测。
In order to further develop the theoretical research of cluster Co_(3)MoS and to investigate the mechanism of isomerization transformation of cluster Co_(3)MoS.Optimization calculation of the clusters was based on density functional theory and transition state theory,using quantum chemistry software and B3LYP/Lanl2dz levels as initial conditions.And the clusters was analyzed by applying thermodynamic and chemical kinetic methods.The results show that each isomerization reaction of cluster Co_(3)MoS is mainly in the forward reaction direction,and TS^(3(2)→1(4))isomerization reaction is the easiest to be transformed,TS^(2(4)→1(2))reaction is the most difficult to be transformed,and the configurations 1^((4)),1^((2)),2^((4)),2^((2)),3^((4)),3^((2))can be steadily existed;the 3^((2))→1^((4))isomerization reaction is the most radically transformed,which limit is the largest than the other isomerization processes,the 2^((4))→1^((2))reaction consumes the most activation energy in the process of transformation,which is the least radical transformation;we find a link between equilibrium constants and thermodynamic stability of reactants and products;the isomerization reaction of the cluster Co_(3)MoS can be predicted by the functional equation of energy difference and equilibrium constant,the integral form of the van't Hoff equation,and the Gibbs function.
作者
王智瑶
方志刚
秦渝
吴庭慧
吕孟娜
郑新喜
WANG Zhi-yao;FANG Zhi-gang;QIN Yu;WU Ting-hui;LÜ Meng-na;ZHENG Xin-xi(School of Chemical Engineering, University of science and Technology Liaoning, Anshan 114051,China)
出处
《哈尔滨理工大学学报》
CAS
北大核心
2022年第1期149-156,共8页
Journal of Harbin University of Science and Technology
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(202110146027,202010146009,202010146016).
关键词
团簇Co_(3)MoS
过渡态
活化能
平衡常数
异构化
cluster Co_(3)MoS
transition state
activation energy
equilibrium constant
isomerization
