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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Trimethylamine/Sulfuric Acid/Water Clusters: A Matrix Isolation Infrared Study
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Trimethylamine/Sulfuric Acid/Water Clusters: A Matrix Isolation Infrared Study

机译：三甲胺/硫酸/水团簇：基质分离红外研究

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摘要

In continuation of our studies of sulfuric acid H-bonded complexes of atmospheric relevance we report the infrared spectra of the matrix isolated complexes formed between trimethylamine and sulfuric acid. Evidence for proton transfer was anticipated for the present system, as trimethylamine ((CH_3)_3N) is of strong basic nature. However, the spectra of this system are complicated by the inevitable presence water in the vapor and in the matrix, resulting in matrix layers containing three species capable of forming H-bonded complexes. The complex formed between trimethylamine and sulfuric acid is of ionic character due to proton transfer of the H~+ proton from sulfuric acid to (CH_3)_3N to form a new N?H bond and the replacement of the intramolecular O?H bond in H_2SO_4 by a strong intermolecular N?H…O hydrogen bond. The complex is further stabilized by hydration. The skeletal modes show clear bisulfate related bands and are only slightly affected by hydration. The ν(OH) region shows a rich band scheme, best explained by a structure involving (at least) three H_2O molecules. A broad spectral feature spanning the 1700?500 cm~(?1) is assigned, in analogy to previous studies to a double-well potential quasi-symmetric, Zundel-like, ionic species with a (CH_3)_3?N…H~+…N?(CH_3)_3 configuration. A band in the skeletal S=O stretch spectral region may be assigned to hydrated sulfate as its counterion.
机译：在继续研究与大气相关的硫酸氢键结合的配合物时，我们报告了三甲胺和硫酸之间形成的基质分离的配合物的红外光谱。由于三甲胺（（CH_3）_3N）具有很强的碱性，因此在本系统中可以预见到质子转移的证据。然而，该系统的光谱由于蒸气和基质中不可避免地存在水而变得复杂，从而导致基质层包含三种能够形成氢键复合物的物质。三甲胺与硫酸之间形成的配合物具有离子性，这是由于H〜+质子从硫酸到（CH_3）_3N的质子转移形成新的N？H键，以及取代了H_2SO_4中的分子内O？H键。通过强大的分子间N？H…O氢键。复合物通过水合进一步稳定。骨骼肌模式显示出清晰的硫酸氢盐相关带，并且受水合影响很小。 ν（OH）区显示出一个富带方案，最好用包含（至少）三个H_2O分子的结构来解释。与以前的研究类似，将一个跨越1700-500 cm〜（？1）的宽光谱特征分配给具有（CH_3）_3？N ... H〜 +…N？（CH_3）_3配置。骨架S ＝ O拉伸光谱区域中的带可以被分配给水合硫酸盐作为其抗衡离子。

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