Electronic structure effects on the double proton transfer reactions: a case study for substituted formic acid dimer

IF 3.8 Q2 CHEMISTRY, PHYSICAL
Mokshi Sharma , Princy Jarngal , Nayan Prakash , Dhiksha Sharma , Subrata Banik , Tapta Kanchan Roy
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Abstract

A comprehensive theoretical study to understand the changes in the electronic structures and their effects on promoter modes for double proton transfer reaction in bare and substituted formic acid dimer (FAD) is presented. In FAD, the dimer-stretch acts as a promoter mode which modulates the effective barrier to proton transfer reactions. Motivated by the fact that the modifications in the electron densities of the system significantly affect the proton transfer process and reaction barrier, the topology of the reactions is investigated by perturbing the electronic environment by substituting the terminal hydrogens attached to the carbon atoms of FAD with electron-donating (ed-) and withdrawing (ew-) groups. The variations in the electronic structure along the intrinsic reaction coordinate (IRC) are examined and compared for three systems: FAD, ed-FAD, and ew-FAD. Quantum mechanical calculations using the B3LYP and MP2 methods were performed to investigate structural features, charge distribution, and natural bond orbital (NBO) analysis, to comprehend the essential electronic distributional changes throughout the reaction. Additionally, reaction force analysis was conducted to gain insights into the electronic activities occurring along the reaction pathway. Among the three systems studied, ed-FAD exhibits the lowest activation energy for the double proton transfer reaction, followed by FAD and ew-FAD, accompanied by several distinct characteristic changes in their electronic and vibrational structures. Substitutions modulated the extent of electron delocalization from the acceptor lone pair to the antibonding orbital of the covalent bond between donor and hydrogen atoms. Reaction force analysis also revealed that reaction work (W) associated with the activation energy is much lower for ed-FAD compared to FAD and ew-FAD.

Abstract Image

电子结构对双质子转移反应的影响:取代甲酸二聚体的个案研究
本文对裸甲酸和取代甲酸二聚体(FAD)中电子结构的变化及其对双质子转移反应启动子模式的影响进行了全面的理论研究。在FAD中,二聚体拉伸作为启动子模式调节质子转移反应的有效屏障。考虑到系统电子密度的改变会显著影响质子转移过程和反应势垒,本文通过扰动电子环境,用给电子基团(ed-)和吸电子基团(ew-)取代FAD连接在碳原子上的末端氢,研究了反应的拓扑结构。考察并比较了FAD、ed-FAD和ew-FAD三种体系在本征反应坐标(IRC)上的电子结构变化。利用B3LYP和MP2方法进行了量子力学计算,研究了结构特征、电荷分布和自然键轨道(NBO)分析,以了解整个反应过程中基本的电子分布变化。此外,还进行了反作用力分析,以深入了解沿反应途径发生的电子活动。在所研究的三种体系中,ed-FAD的双质子转移反应活化能最低,其次是FAD和ew-FAD,它们的电子结构和振动结构发生了一些明显的特征变化。取代调节了电子从受体孤对到供体和氢原子之间共价键反键轨道的离域程度。反作用力分析还表明,与FAD和ew-FAD相比,ed-FAD与活化能相关的反应功(W)要低得多。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Chemical Physics Impact
Chemical Physics Impact Materials Science-Materials Science (miscellaneous)
CiteScore
2.60
自引率
0.00%
发文量
65
审稿时长
46 days
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