Infrared Spectrum of the Hydrated Proton in Water.
Infrared Spectrum of the Hydrated Proton in Water.
复制标题
DOI：
10.1021/jz101536b
复制
发表时间：
2011-01
期刊：
影响因子：
--
通讯作者：
Jianqing Xu;Yong Zhang;G. Voth
中科院分区：
文献类型：
--
作者：
Jianqing Xu;Yong Zhang;G. Voth
反应分子动力学模拟已被用来计算不同浓度的酸性 HCl 溶液的红外 (IR) 光谱，目的是更好地了解大量水中水合过量质子的光谱特征。为了结合水合质子的基本物理原理，我们使用专门的自洽迭代多态经验价键（SCI-MS-EVB）方法进行了模拟，该方法是多构型（反应性）分子动力学的一种形式。去除纯水吸收背景后，计算的差异光谱与先前的实验结果非常吻合。酸性红外光谱中的连续宽吸收带首次根据动态畸变本征阳离子 H9O4(+) 的概念进行解释，已被证明可以为液态水中水合过量质子的电荷缺陷特征提供最准确的描述。
Reactive molecular dynamics simulations have been utilized to calculate the infrared (IR) spectra of acidic HCl solutions of varying concentration with the goal of achieving a better understanding of the spectral features of the hydrated excess protons in bulk water. To incorporate the essential physics of the hydrated proton, we carried out the simulations using the specialized self-consistent iterative multistate empirical valence bond (SCI-MS-EVB) method, which is a form of multiconfigurational (reactive) molecular dynamics. After the pure water absorption background was removed, the calculated difference spectra are in good agreement with prior experimental results. The continuous broad absorption band in the acidic IR spectrum is, for the first time, interpreted based on the concept of a dynamically distorted Eigen cation, H9O4(+), which has been shown to provide the most accurate description for the charge defect character of the hydrated excess proton in liquid water.