Abu-samha Mahmoud, Børve Knut J
Department of Chemistry, University of Bergen , Allégaten 41, NO-5007 Bergen, Norway.
J Phys Chem A. 2014 Aug 28;118(34):6900-7. doi: 10.1021/jp504883r. Epub 2014 Aug 18.
HCl dissociation in methanol clusters is studied by ab initio molecular dynamics simulations and experimentally by X-ray photoelectron spectroscopy. From theoretical simulations of HCl in oligomers and medium-sized clusters of methanol, two states of solvation are identified for HCl: an intermediate proton-sharing (ion pair) state and a fully dissociated state. Lowering the temperature from 150 to 100 K is found to promote full dissociation over the proton-sharing state. The dissociation of HCl is well reflected in the experimental chlorine 2p photoelectron spectrum recorded for a beam of clusters formed by adiabatic expansion of the vapor over a solution of HCl in methanol. In order to reproduce the observed Cl 2p spectrum by means of theoretical line-shape modeling, one needs to take into account both the intermediate proton-sharing state and the fully dissociated state.
通过从头算分子动力学模拟对盐酸（HCl）在甲醇团簇中的离解进行了研究，并通过X射线光电子能谱进行了实验研究。从对HCl在甲醇低聚物和中等尺寸团簇中的理论模拟中，确定了HCl的两种溶剂化状态：中间质子共享（离子对）状态和完全离解状态。发现将温度从150 K降低到100 K会促进HCl从质子共享状态完全离解。HCl的离解在通过将蒸汽在HCl的甲醇溶液上进行绝热膨胀形成的团簇束记录的实验氯2p光电子能谱中得到了很好的体现。为了通过理论线形建模重现观察到的Cl 2p光谱，需要同时考虑中间质子共享状态和完全离解状态。
