A reaction density functional theory study of solvent effects on keto-enol tautomerism and isomerization in pyruvic acid

doi:10.1016/j.cjche.2020.08.003

Abstract

Abstract: It is important to study the solvent effect on keto-enol tautomerism that has applications in many areas of chemical engineering. In this work, we use a multiscale reaction density functional theory (RxDFT) to study the keto-enol tautomerism and isomerization of pyruvic acid. The results show that both effects of solvation and water assistance could reduce the reaction barriers. The water molecule participates the reaction as a catalyst to accept/give the protons with forming a hexagonal ring in the transition state. As a result of this temporary and intermediate hexagonal ring, the solute configuration undergoes a small variation during the reaction, giving a diminished contribution to the intrinsic reaction free energy. The solvent distribution shows a local ordering behavior near the solute that also reduces the contribution of solvation effect to the reaction barrier. Water assistance plays a major role in both pre-reaction and post-reaction process. In terms of the driving force for the reaction, the effects of both solvation and water assistance are important.

Key words: Solvent effect, Reaction density functional theory, Pyruvic acid, Tautomerism, Isomerization

摘要： It is important to study the solvent effect on keto-enol tautomerism that has applications in many areas of chemical engineering. In this work, we use a multiscale reaction density functional theory (RxDFT) to study the keto-enol tautomerism and isomerization of pyruvic acid. The results show that both effects of solvation and water assistance could reduce the reaction barriers. The water molecule participates the reaction as a catalyst to accept/give the protons with forming a hexagonal ring in the transition state. As a result of this temporary and intermediate hexagonal ring, the solute configuration undergoes a small variation during the reaction, giving a diminished contribution to the intrinsic reaction free energy. The solvent distribution shows a local ordering behavior near the solute that also reduces the contribution of solvation effect to the reaction barrier. Water assistance plays a major role in both pre-reaction and post-reaction process. In terms of the driving force for the reaction, the effects of both solvation and water assistance are important.

关键词: Solvent effect, Reaction density functional theory, Pyruvic acid, Tautomerism, Isomerization

Changjie Lu, Weiqiang Tang, Zijiang Dou, Peng Xie, Xiaofei Xu, Shuangliang Zhao. A reaction density functional theory study of solvent effects on keto-enol tautomerism and isomerization in pyruvic acid[J]. Chinese Journal of Chemical Engineering, 2021, 29(3): 10-16.

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