Unidad Asociada Química-Física UCM-IEM/CSIC, Dept. Química Física I, Universidad Complutense de Madrid, Avda Complutense s/n, 28040 Madrid, Spain.
Phys Chem Chem Phys. 2010 May 14;12(18):4617-24. doi: 10.1039/b924890k. Epub 2010 Mar 18.
Theoretical calculations at the B3LYP/aug-cc-pVQZ level are performed on ternary clusters of water, hydrogen chloride and nitric acid to predict their IR and MW spectra. The main IR spectral features and their changes in a set of 15 selected clusters are analyzed in terms of the different hydrogen bonding characteristics of the aggregates. The formation of these clusters in laboratory experiments and their possible identification based on their infrared and microwave spectral properties are discussed. Based on a calculation of the Gibbs free-energy of formation of the clusters from their monomers, the population distribution of the molecules at atmospherically relevant temperatures is evaluated, and the IR spectra of the composed mixture are predicted. The variations of specific spectral features with temperature are assessed, and the possible observation of these features is proposed as a means to detect the existence of these clusters, as well as an indication of the temperature of the corresponding atmospheric sample.
在 B3LYP/aug-cc-pVQZ 水平上进行了理论计算，以预测水、氯化氢和硝酸的三元团簇的红外和微波光谱。根据聚集体的不同氢键特征，分析了一组 15 个选定团簇的主要红外光谱特征及其变化。讨论了这些团簇在实验室实验中的形成及其可能根据其红外和微波光谱特性进行的鉴定。基于从单体形成团簇的吉布斯自由能的计算，评估了在大气相关温度下分子的种群分布，并预测了组成混合物的红外光谱。评估了特定光谱特征随温度的变化，并提出了观察这些特征的可能性，作为检测这些团簇存在的一种手段，以及对应大气样本温度的指示。
