作者:王智瑶，方志刚，秦渝，吴庭慧，吕孟娜，郑新喜
Authors:\n\tWANG Zhi-yao,FANG Zhi-gang,QIN Yu,WU Ting-hui,Lv Meng-na,ZHENG Xin-xi\n
摘要:摘要:为了进一步完善团簇Co₃MoS的理论研究，同时也为研究团簇Co₃MoS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Co₃MoS各异构化反应以正反应方向为主，TS3⁽²⁾ →1⁽⁴⁾异构化反应最易发生转化，TS2⁽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Co₃MoS异构化反应进行预测。
Abstract:Abstract:In order to further develop the theoretical research of cluster Co₃MoS and to investigate the mechanism of isomerization transformation of cluster Co₃MoS. 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 Co₃MoS is mainly in the forward reaction direction, and TS3⁽²⁾→1⁽⁴⁾isomerization reaction is the easiest to be transformed, TS2⁽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 Co₃MoS 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.

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