二维CrPS4异构化反应的热力学与动力学研究

doi:10.16088/j.issn.1001-6600.2023040701

摘要/Abstract

摘要： 本文依据拓扑学原理,从热力学和动力学角度出发,利用密度泛函理论,对团簇CrPS₄的异构化反应进行研究。结果表明:团簇CrPS₄的异构化反应过程主要依赖于非金属原子之间键的断裂和生成,异构化反应的生成物稳定性越好,反应物与生成物稳定性相差越大,异构化反应的平衡常数就越大,反应进行得就越完全;反应物越不稳定,本身含能就越高,跃迁到活化状态所需要的活化能就越低,就越容易发生异构化反应;所有构型均能通过异构化反应转化为稳定性较好的构型1⁽⁴⁾、 1⁽²⁾、 3⁽⁴⁾、 2⁽²⁾和2⁽⁴⁾。 5⁽⁴⁾-2⁽⁴⁾和 6⁽⁴⁾-1⁽⁴⁾的反应速度最快且进行得最彻底。熵增反应正反应的指前因子大于逆反应指前因子,对正反应速度促进作用更大,这一差值使得异构化反应越易进行。

关键词: 团簇CrPS₄, 异构化, 密度泛函, 活化能, 指前因子

Abstract: The article investigates the isomerisation reaction of clusters based on the topological principle, using density general function theory, from the perspective of thermodynamics and kinetics, and finally obtains the following conclusions: the process of isomerisation reaction of clusters CrPS₄ mainly depends on the breaking and formation of bonds between non-metallic atoms. The better the stability of the products of the isomerisation reaction, the greater the difference in stability between the reactants and the products, the greater the equilibrium constant of the isomerisation reaction and the more completely the reaction proceeds. The more unstable the reactants are, the higher their energy content and the lower the activation energy required to leap to the activated state, the more likely the isomerisation reaction will occur. All configurations are converted to the more stable configurations 1⁽⁴⁾, 1⁽²⁾, 3⁽⁴⁾, 2⁽²⁾ and 2⁽⁴⁾ by isomerisation reactions. 5⁽⁴⁾-2⁽⁴⁾ and 6⁽⁴⁾-1⁽⁴⁾ are the fastest and most complete reactions. The entropy-increasing positive reaction has a greater finger front factor than the reverse reaction finger front factor, contributing more to the positive reaction rate, and this difference makes the isomerisation reaction easier to carry out.

Key words: cluster CrPS₄, isomerization, density functional theory, activation energy, preexponential factor

中图分类号: O641.12

刘立娥, 方志刚, 宋静丽, 原琳, 魏代霞. 二维CrPS₄异构化反应的热力学与动力学研究[J]. 广西师范大学学报（自然科学版）, 2023, 41(6): 122-131.

LIU Li'e, FANG Zhigang, SONG Jingli, YUAN Lin, WEI Daixia. Thermodynamics and Kinetics of Isomerization Reaction of Two Dimensional CrPS₄[J]. Journal of Guangxi Normal University(Natural Science Edition), 2023, 41(6): 122-131.

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二维CrPS₄异构化反应的热力学与动力学研究

Thermodynamics and Kinetics of Isomerization Reaction of Two Dimensional CrPS₄

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