Bonechi Marco, Innocenti Massimo, Vanossi Davide, Fontanesi Claudio
Department of Chemistry, University of Firenze, via della Lastruccia 3, 50019 Sesto Fiorentino, Italy.
Department of Engineering "Enzo Ferrari", University of Modena and Reggio Emilia, Via Vivarelli 10, 41125 Modena, Italy.
J Phys Chem A. 2021 Jan 14;125(1):34-42. doi: 10.1021/acs.jpca.0c07702. Epub 2020 Dec 22.
The Kane-Maguire polymerization mechanism is disassembled at a molecular level by using DFT-based quantum mechanical calculations. Resorcinol electropolymerization is selected as a case study. Stationary points (transition states and intermediate species) leading to the formation of the dimer are found on the potential energy surface (PES), and elementary reactions involved in the dimer formation are characterized. The latter allow to further propagate the polymerization chain reaction, when applied recursively. In this paper, the fundamental role of the sulfate anion (a typical base electrolyte) is addressed. Investigation of the PES in terms of both stationary-state properties and of ab initio molecular dynamics results (dynamic reaction coordinate) allows the appreciation in detail of the critical role of the base electrolyte anion in making the proton dissociation from the initial radical ion, a feasible (downhill in energy) process.
通过基于密度泛函理论（DFT）的量子力学计算，在分子水平上拆解了凯恩 - 马奎尔聚合机理。选择间苯二酚电聚合作为案例研究。在势能面（PES）上找到了导致二聚体形成的驻点（过渡态和中间物种），并对二聚体形成过程中涉及的基元反应进行了表征。当递归应用时，后者可使聚合链反应进一步传播。本文探讨了硫酸根阴离子（一种典型的碱性电解质）的基本作用。从稳态性质和从头算分子动力学结果（动态反应坐标）两方面对PES进行研究，能够详细认识到碱性电解质阴离子在使质子从初始自由基离子解离这一过程中所起的关键作用，该过程在能量上是可行的（能量下坡）。
