Theoretical study on the interlay of hydrogen bonds in the trimers involving HCN and water |
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| Authors: | Qingzhong Li Xilin Wang Jianbo Cheng Wenzuo Li Baoan Gong Jiazhong Sun |
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| Institution: | 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. Key Laboratory for Supramolecular Structure and Materials of Ministry of Education, Jilin University, Changchun 130012, People's Republic of China |
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| Abstract: | In this study, the hydration of hydrogen cyanide (HCN) has been investigated by means of quantum chemical ab initio calculations at the MP2/6‐311++G(3df,2p) level. Various HCN· · ·( H2O)2 and (HCN)2· · ·H2O complexes were optimized. Geometrics and energetics in these complexes have been analyzed. The hydration of the H atom leads to an elongation of the N?C and C? H bonds, whereas the hydration of the N atom results in a contraction of the N?C bond and a little elongation of the C? H bond. The interaction energy between each molecule pair in the trimers (except in HCN? H2O? H2O trimer) is increased relative to that in the respective dimer. The cooperativity of hydrogen bond in HCN? H2O? H2O trimer plays a negative contribution to the total interaction energy of the complex, whereas that in the other trimers is a positive contribution. Geometry and energy in H2O? H2OO? HCN? H2O tetramer have also been analyzed. The binding energies in the trimers and tetramer have been studied by means of many‐body interaction analysis. The mechanism of HCN hydration was suggested. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 |
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| Keywords: | hydrogen cyanide hydration cooperativity three‐body interaction two‐body interaction |
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