Theoretical Messenger Spectroscopy of Microsolvated Hydronium and Zundel Cations
Theoretical Messenger Spectroscopy of Microsolvated Hydronium and Zundel Cations
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DOI：
10.1002/anie.201001672
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发表时间：
2010-01-01
影响因子：
16.6
通讯作者：
Mathias, Gerald
中科院分区：
文献类型：
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作者：
Baer, Marcel;Marx, Dominik;Mathias, Gerald
在水溶液中最普遍存在的离子是溶剂化质子，H+（aq），其从溶液化学到酶促过程具有根本重要性。两种典型的质子化水络合物，H3 O+（水合氢离子）和H5 O2+（Zundel阳离子），不仅是凝聚相中更复杂的瞬态网络的基本组成部分，[1]而且在诸如团簇科学和大气化学等领域拥有自己的权利。因此，有限H+（H2O）n复合物一直是众多研究的焦点。[2-10]振动光谱学的改进，特别是基于信使预解离和多光子解离的复杂作用光谱学方法，使人们对这些物种有了前所未有的了解。[11然而，信使光谱的解释绝不是简单的，因为母体分子与标记物质（如H2，Ar或Ne）的相互作用。在开创性的实验中，YT Lee和同事通过H2微溶剂化研究了3100 cm-1以上光谱范围内的水合氢离子和Zundel阳离子。[3，13，14]这些光谱表明信使物质与这些阳离子之间的相互作用显着修改了光谱。最近的高分辨率振动predissociation测量使用Ar或Ne加合物现在访问完整的红外指纹区域下降到600 cm-1。[7，15-18]然而，重要的光谱特征，如质子转移模式的特征双带或OH伸缩区域中的带数，差异很大，并且在很大程度上取决于所采用的实验方法。[3-5在全维量子动力学计算（MCTDH）中，最近H. D. Meyer和同事的研究，这解释了前面提到的1000 cm ²附近的挑战性双带是费米共振。[9]然而，这种非常精确的
Among the most ubiquitous ions in aqueous solutions are solvated protons, H+(aq), which are of fundamental importance from solution chemistry to enzymatic processes. The two archetypal protonated water complexes, the H3O+(hydronium ion) and H5O2+(Zundel cation), are not only the basic building blocks of more complex transient networks in condensed phases,[1] but have a right of their own in fields such as cluster science and atmospheric chemistry, to name but two. Therefore, finite H+(H2O) n complexes have been the focus of a plethora of investigations.[2–10] Improvements in vibrational spectroscopy, and in particular sophisticated action spectroscopic methods based on messenger predissociation and multiphoton dissociation, allow unprecedented insights into such species.[11, 12] However, the interpretation of messenger spectra is by no means straightforward owing to interactions of the parent molecules with tagging species, such as H2, Ar, or Ne.In pioneering experiments, YT Lee and co-workers studied the hydronium and Zundel cations in the spectral range above 3100 cmÀ1 by H2 microsolvation.[3, 13, 14] These spectra showed that interactions between the messenger species and these cations significantly modify the spectra. Recent high-resolution vibrational predissociation measurements using Ar or Ne adducts now access the full IR fingerprint region down to 600 cmÀ1.[7, 15–18] However, important spectral features, such as the characteristic double band of the proton-transfer mode or the number of bands in the OH stretching region, differ significantly and depend heavily on the experimental method that is employed.[3–5, 13, 16] In a tour de force full-dimensional quantum dynamics calculation (MCTDH), the comprehensive spectral assignment of the bare Zundel cation has been recently accomplished by H.-D. Meyer and co-workers, which explains the aforementioned challenging double band near 1000 cmÀ1 as being a Fermi resonance.[9] However, such very precise