Bottom-Up View of Water Network-Mediated CO_2 Reduction Using Cryogenic Cluster Ion Spectroscopy and Direct Dynamics Simulations (Invited Article, Feature Cover Article)
Bottom-Up View of Water Network-Mediated CO_2 Reduction Using Cryogenic Cluster Ion Spectroscopy and Direct Dynamics Simulations (Invited Article, Feature Cover Article)
复制标题
使用低温团簇离子光谱和直接动力学模拟实现水网络介导的 CO_2 还原的自下而上视图（特邀文章，专题封面文章）
DOI：
10.1021/jp209493v
复制
发表时间：
2012
影响因子：
--
通讯作者：
et al.
中科院分区：
文献类型：
--
作者：
Kristin J.Breen;et al.
溶液中化学反应的过渡态通常是通过溶剂和反应物之间的热能交换来获得的。因此，一系列反应体系以一种不连贯的方式接近反应物和周围溶剂的过渡态构型，这不利于直接的实验观察。在这里，我们描述了当六个水分子组成的网络中介将高活性的“水合电子”捕获到中性二氧化碳分子上形成自由基阴离子时，气相团簇化学如何提供起作用的微观机制的详细图像。放热反应是从介稳中间体通过选择性激发反应物CO2或水网络来触发的，产物簇的蒸发分解证明了这一点。用从头算分子动力学方法对带能的Co2·(H2O)6团簇进行了分子动力学模拟，揭示了在溶液中电子转移动力学的Marcus理论中所隐含的详细的溶剂涨落。
The transition states of a chemical reaction in solution are generally accessed through exchange of thermal energy between the solvent and the reactants. As such, an ensemble of reacting systems approaches the transition state configuration of reactant and surrounding solvent in an incoherent manner that does not lend itself to direct experimental observation. Here we describe how gas-phase cluster chemistry can provide a detailed picture of the microscopic mechanics at play when a network of six water molecules mediates the trapping of a highly reactive “hydrated electron” onto a neutral CO2molecule to form a radical anion. The exothermic reaction is triggered from a metastable intermediate by selective excitation of either the reactant CO2or the water network, which is evidenced by the evaporative decomposition of the product cluster. Ab initio molecular dynamics simulations of energized CO2·(H2O)6–clusters are used to elucidate the nature of the network deformations that mediate intracluster electron capture, thus revealing the detailed solvent fluctuations implicit in the Marcus theory for electron-transfer kinetics in solution.