Exploring the Solvation of Acetic Acid in Water Using Liquid Jet X-ray Photoelectron Spectroscopy and Core Level Electron Binding Energy Calculations
Exploring the Solvation of Acetic Acid in Water Using Liquid Jet X-ray Photoelectron Spectroscopy and Core Level Electron Binding Energy Calculations
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DOI：
10.1021/acs.jpcb.1c03520
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发表时间：
2021-08-02
影响因子：
3.3
通讯作者：
Hemminger, John C.
中科院分区：
文献类型：
--
作者：
Bruce, Jared P.;Zhang, Kimberly;Hemminger, John C.
液体喷射 X 射线光电子能谱用于研究溶剂化效应引起的大量水溶液中乙酸局部电子结构的变化。这些效应表现为乙酸的甲基碳和羧基碳之间的碳结合能 (Delta BE) 差异的变化。此外，分子动力学模拟，加上第一溶剂化球的相关电子结构计算，可以深入了解与羧基直接相互作用的水分子的数量，这些水分子是匹配光电子能谱实验中的 Delta BE 所需的。该比较表明，第一个溶剂化壳层中的单个水分子描述了乙酸的光电子 Delta BE，而水溶液中的共轭碱乙酸盐需要至少 20 个水分子。
Liquid jet X-ray photoelectron spectroscopy was used to investigate changes in the local electronic structure of acetic acid in the bulk of aqueous solutions induced by solvation effects. These effects manifest themselves as shifts in the difference in the carbon is binding energy (Delta BE) between the methyl and carboxyl carbons of acetic acid. Furthermore, molecular dynamics simulations, coupled with correlated electronic structure calculations of the first solvation sphere, provide insight into the number of water molecules directly interacting with the carboxyl group that are required to match the Delta BE from the photoelectron spectroscopy experiments. This comparison shows that a single water molecule in the first solvation shell describes the photo-electron Delta BE of acetic acid while at least 20 water molecules are required for the conjugate base, acetate, in aqueous solutions.