Ab Initio Study of the Structure, Cooperativity, and Vibrational Properties in the Mixed Hydrogen-Bonded Trimers of Hydrogen Isocyanide and Water

作者：Li, Qingzhong^*; Jiang, Lixia; Wang, Xilin; Li, Wenzuo; Cheng, Jianbo; Sun, Jiazhong

来源：International Journal of Quantum Chemistry, 2011, 111(5): 1072-1080.

DOI：10.1002/qua.22469

• hydrogen bond
• hydrogen isocyanide
• water
• cooperativity
• many-body interaction

The five trimers of H2O center dot center dot center dot HNC center dot center dot center dot H2O, H2O center dot center dot center dot H2O center dot center dot center dot HNC, HNC center dot center dot center dot H2O center dot center dot center dot H2O, H2O center dot center dot center dot HNC center dot center dot center dot HNC, and HNC center dot center dot center dot HNC center dot center dot center dot 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 center dot center dot center dot H2O center dot center dot center dot 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 center dot center dot center dot HNC center dot center dot center dot HNC trimer are larger than those in the HNC center dot center dot center dot HNC center dot center dot center dot H2O trimer. The NH stretch frequency has a blue shift for the terminal HNC molecule in the HNC center dot center dot center dot H2O center dot center dot center dot H2O and HNC center dot center dot center dot HNC center dot center dot center dot 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.

• 出版日期2011-4
• 单位河北北方学院; 烟台大学