Uras-Aytemiz Nevin, Devlin J Paul, Sadlej Joanna, Buch Victoria
Department of Chemistry, Suleyman Demirel University, 32260 Isparta, Turkey.
J Phys Chem B. 2006 Nov 2;110(43):21751-63. doi: 10.1021/jp062753z.
Condensed-phase solvation of HCl on and within methanol nanoparticles was investigated by Fourier transform infrared (FTIR) spectroscopy, on-the-fly molecular dynamics as implemented in the density functional code Quickstep (which is part of the CP2K package), and ab initio calculations. Adsorption and solvation stages are identified and assigned with the help of calculated infrared spectra obtained from the simulations. The results have been further checked with MP2-level ab initio calculations. The range of acid solvation states extends from the single-coordinated slightly stretched HCl to proton-sharing with Zundel-like methanol O...H+...X- states, and finally to MeOH2+...Cl- units with full proton transfer. Furthermore, once the proton moves to methanol, it is mobilized along methanol molecular chains. Since the proton dynamics reflects the evolving local structures, the "proton" spectra display broad bands usually with underlying continua.
通过傅里叶变换红外（FTIR）光谱、密度泛函代码Quickstep（CP2K软件包的一部分）中实现的实时分子动力学以及从头算计算，研究了HCl在甲醇纳米颗粒上及其内部的凝聚相溶剂化。借助模拟得到的计算红外光谱识别并确定了吸附和溶剂化阶段。结果通过MP2水平的从头算计算进行了进一步验证。酸溶剂化状态的范围从单配位的轻微拉伸HCl到与类祖德甲醇O...H⁺...X⁻状态的质子共享，最终到具有完全质子转移的MeOH₂⁺...Cl⁻单元。此外，一旦质子转移到甲醇中，它就会沿着甲醇分子链移动。由于质子动力学反映了不断演变的局部结构，“质子”光谱通常显示宽带并伴有连续谱。
