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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >On the Intramolecular Origin of the Blue Shift of A-H Stretching Frequencies: Triatomic Hydrides HAX
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On the Intramolecular Origin of the Blue Shift of A-H Stretching Frequencies: Triatomic Hydrides HAX

机译：关于A-H拉伸频率蓝移的分子内起源：三原子氢化物HAX

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摘要

A series of intermolecular complexes formed between the triatomic hydrides HAX and various interaction partners are investigated computationally aiming (1) to demonstrate that either an appearance or nonappearance of a blue shift of the A-H stretching frequency is directly related to the sign of the intramolecular coupling that exists between the two degrees of freedom, the A-H andA-X bond lengths, and (2) to offer the following conjecture: the theoretical protonation of a triatomic neutral molecule HAX at the site X is a simple and rather efficient probe of a red or blue shift that the stretching frequency (A-H) undergoes upon complex formation regardless of whether this bond is directly involved in hydrogen bonding or not. In other words, to predict whether this A-H bond is capable to display a blue or red shift of (A-H), it suffices to compare the equilibrium structures and vibrational spectra of a given molecule with its protonated counterpart. The two above goals are achieved invoking a series of 11 triatomic molecules: HNO, HSN, HPO, and HPS characterized by a negative intramolecular coupling; HON and HNS as intermediate cases; and HOF, HOCl, HCN, HNC, and HCP with a positive intramolecular coupling. For these purposes, the latter molecules are investigated at the MP2/6-311++G(2p,2d) level in the neutral and protonated HAXH+ forms as well as their complexes with H2O and with the fluoromethanes H3CF, H2CF2, and HCF3.
机译：在计算上研究了三原子氢化物HAX与各种相互作用配体之间形成的一系列分子间复合物，目的是（1）证明AH拉伸频率蓝移的出现或不出现与分子内偶联的符号直接相关。存在于两个自由度之间，即AH和A-X键长度，以及（2）提供以下推测：在位点X处的三原子中性分子HAX的理论质子化是对红色或拉伸频率（AH）在复合物形成时经历的蓝移，无论该键是否直接参与氢键。换句话说，要预测此A-H键是否能够显示（A-H）的蓝移或红移，只需将给定分子与其质子化的对应物的平衡结构和振动光谱进行比较即可。通过调用一系列11个三原子分子（分子特征为负分子内的HNO，HSN，HPO和HPS）可以实现上述两个目标。 HON和HNS作为中间案例; HOF，HOCl，HCN，HNC和HCP具有积极的分子内偶联。为此目的，以中性和质子化的HAXH +形式及其与H2O以及与氟代烃H3CF，H2CF2和HCF3的配合物，以MP2 / 6-311 ++ G（2p，2d）水平研究了后者的分子。

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