{"title":"全 (24) 维中 OH- + CH3CH2Cl SN2 和 E2 反应的基于势能面的高级分析动力学","authors":"Andras B. Nacsa, Csenge Tokaji, Gabor Czako","doi":"10.1039/d3fd00161j","DOIUrl":null,"url":null,"abstract":"We develop a coupled-cluster full-dimensional global potential energy surface (PES) for the OH− + CH3CH2Cl reactive system, using the ROBOSURFER program package, which automatically samples configurations along PES-based trajectories as well as performs ab initio computations with MOLPRO and fitting with the monomial symmetrization approach. The analytical PES accurately describes both the bimolecular nucleophilic substitution (SN2) and elimination (E2) channels leading to the Cl− + CH3CH2OH and Cl− + H2O + C2H4 products, respectively, and allows efficient quasi-classical trajectory (QCT) simulations. QCT computations on the new PES provide accurate statistically-converged integral and differential cross sections for the OH− + CH3CH2Cl reaction, revealing the competing dynamics and mechanisms of the SN2 and E2 (anti, syn, β−α transfer) channels as well as various additional pathways leading to induced inversion of the CH3CH2Cl reactant, H-exchange between the reactants, H2O⋯Cl− complex formation, and H2O + CH3CHCl products via proton abstraction.","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":null,"pages":null},"PeriodicalIF":3.3000,"publicationDate":"2024-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"High-level analytical potential-energy-surface-based dynamics of the OH− + CH3CH2Cl SN2 and E2 reactions in full (24) dimensions\",\"authors\":\"Andras B. Nacsa, Csenge Tokaji, Gabor Czako\",\"doi\":\"10.1039/d3fd00161j\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"We develop a coupled-cluster full-dimensional global potential energy surface (PES) for the OH− + CH3CH2Cl reactive system, using the ROBOSURFER program package, which automatically samples configurations along PES-based trajectories as well as performs ab initio computations with MOLPRO and fitting with the monomial symmetrization approach. The analytical PES accurately describes both the bimolecular nucleophilic substitution (SN2) and elimination (E2) channels leading to the Cl− + CH3CH2OH and Cl− + H2O + C2H4 products, respectively, and allows efficient quasi-classical trajectory (QCT) simulations. QCT computations on the new PES provide accurate statistically-converged integral and differential cross sections for the OH− + CH3CH2Cl reaction, revealing the competing dynamics and mechanisms of the SN2 and E2 (anti, syn, β−α transfer) channels as well as various additional pathways leading to induced inversion of the CH3CH2Cl reactant, H-exchange between the reactants, H2O⋯Cl− complex formation, and H2O + CH3CHCl products via proton abstraction.\",\"PeriodicalId\":76,\"journal\":{\"name\":\"Faraday Discussions\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2024-02-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Faraday Discussions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d3fd00161j\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Faraday Discussions","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d3fd00161j","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
我们利用 ROBOSURFER 程序包为 OH- + CH3CH2Cl 反应体系开发了一个耦合簇全维全局势能面 (PES),该程序包可沿着基于 PES 的轨迹自动采样构型,并利用 MOLPRO 和单次对称化方法拟合进行 ab initio 计算。分析型 PES 准确地描述了分别导致 Cl- + CH3CH2OH 和 Cl- + H2O + C2H4 产物的双分子亲核置换(SN2)和消除(E2)通道,并可进行高效的准经典轨迹(QCT)模拟。在新的 PES 上进行的 QCT 计算为 OH- + CH3CH2Cl 反应提供了精确的统计收敛积分和微分截面,揭示了 SN2 和 E2(反、同、β-α 转移)通道的竞争动力学和机制,以及导致 CH3CH2Cl 反应物诱导反转、反应物之间的 H 交换、H2O⋯Cl- 复合物形成和通过质子抽取产生 H2O + CH3CHCl 产物的各种额外途径。
High-level analytical potential-energy-surface-based dynamics of the OH− + CH3CH2Cl SN2 and E2 reactions in full (24) dimensions
We develop a coupled-cluster full-dimensional global potential energy surface (PES) for the OH− + CH3CH2Cl reactive system, using the ROBOSURFER program package, which automatically samples configurations along PES-based trajectories as well as performs ab initio computations with MOLPRO and fitting with the monomial symmetrization approach. The analytical PES accurately describes both the bimolecular nucleophilic substitution (SN2) and elimination (E2) channels leading to the Cl− + CH3CH2OH and Cl− + H2O + C2H4 products, respectively, and allows efficient quasi-classical trajectory (QCT) simulations. QCT computations on the new PES provide accurate statistically-converged integral and differential cross sections for the OH− + CH3CH2Cl reaction, revealing the competing dynamics and mechanisms of the SN2 and E2 (anti, syn, β−α transfer) channels as well as various additional pathways leading to induced inversion of the CH3CH2Cl reactant, H-exchange between the reactants, H2O⋯Cl− complex formation, and H2O + CH3CHCl products via proton abstraction.