Ab initio study of the structure,cooperativity, and vibrational properties in the mixed hydrogen‐bonded trimers of hydrogen isocyanide and water |
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| Authors: | Qingzhong Li Lixia Jiang Xilin Wang Wenzuo Li Jianbo Cheng Jiazhong Sun |
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| Affiliation: | 1. The Laboratory of Theoretical and Computational Chemistry, Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005, People's Republic of China;2. Foreign Language College, Heibei North University, Zhangjiakou 075100, People's Republic of China |
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| Abstract: | The five trimers of H2O···HNC···H2O, H2O···H2O···HNC, HNC···H2O···H2O, H2O···HNC···HNC, and HNC···HNC···H2O have been studied with quantum chemical calculations. Their structures, harmonic vibrational frequencies and interaction energies have been calculated at the B3LYP and MP2 levels with the aug‐cc‐pVDZ and aug‐cc‐pVTZ basis sets. The cooperative effect on these properties has also been studied quantitatively. For HNC:(H2O)2 systems, the cyclic H2O···H2O···HNC trimer is most stable with an interaction energy of ?16.01 kcal/mol and a large cooperative energy of ?3.25 kcal/mol at the MP2/aug‐cc‐pVTZ level. For H2O:(HNC)2 systems, the interaction energy and cooperative energy in the H2O···HNC···HNC trimer are larger than those in the HNC···HNC···H2O trimer. The NH stretch frequency has a blue shift for the terminal HNC molecule in the HNC···H2O···H2O and HNC···HNC···H2O trimers and a red shift in other cases. A many‐body analysis has also been performed to understand the interaction energies in these hydrogen‐bonded clusters. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 |
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| Keywords: | hydrogen bond hydrogen isocyanide water cooperativity many‐body interaction |
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