School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
J Chem Phys. 2009 Dec 14;131(22):224307. doi: 10.1063/1.3268502.
The morphological development of the hydrogen bond network in the protonated hydrogen fluoride clusters, H(+)(HF)(n) (n=2-9), is investigated in detail by ab initio methods. We find a dominance of the linear morphology, which is energetically well separated from the other minimum energy morphologies of the clusters. The geometry for these clusters shows a pattern due to the cooperativity effect prevalent in the hydrogen bonds, as a result of the difference in electronegativities of hydrogen and fluorine atom in the HF molecule. The variations in the covalent HF and hydrogen bond distances in the clusters are in turn reflected in the vibrational spectra. Distinct HF stretching modes for the linear and ring with tail structures were identified. We have discussed the signature peaks for the two possible ion-core morphologies present in the clusters. The highly corrosive nature of HF makes it difficult to study using experiments. We, thus, believe that our structure and vibrational spectra calculations would be useful in understanding the key features in these systems.
通过从头算方法详细研究了质子化氟化氢团簇 H(+)(HF)(n)（n=2-9）中氢键网络的形态发展。我们发现线性形态占主导地位，其能量与团簇的其他最小能量形态明显分离。这些团簇的几何形状由于 HF 分子中氢和氟原子的电负性差异而存在协同效应，呈现出一种模式。在团簇中，共价 HF 和氢键距离的变化反映在振动光谱中。线性和带尾环状结构的 HF 伸缩模式是不同的。我们讨论了两种可能的离子核形态在团簇中的特征峰。HF 的高腐蚀性使其难以通过实验进行研究。因此，我们认为我们的结构和振动光谱计算将有助于理解这些系统中的关键特征。
