Theoretical Study of Small Water Clusters of Sulfur Dioxide

• 作 者: 赵亚英 曾永平 张锡辉 陶福明
• 机 构: Research Center of Environmental Engineering and Management,Graduate School at Shenzhen, Tsinghua Un
• 出 处: 结构化学
• 发表日期: 2010年04期
• 关键词: intermolecular complexes Sulfur spectroscopic stretching Infrared assignment ret

The intermolecular clusters of sulfur dioxide with water, SO2(H2O)n (n = 2～5), are studied by using B3LYP density functional theory and MP2 ab initio methods along with the large basis sets (6-311++G(d,p) and aug-cc-pVDZ). The equilibrium geometries, intermolecular binding energies, and anharmonic frequencies of the clusters are calculated and compared with those of pure water clusters and available experiments. SO2 tends to form cyclic hydrogen-bonded complexes with two or three water molecules. In the larger clusters, however, water molecules begin to retain the structure of pure water clusters and segregate from SO2. Infrared absorption assignments for the small clusters are discussed to resolve a possible incorrect assignment in a recent spectroscopic experiment on the clusters.

The intermolecular clusters of sulfur dioxide with water, SO2 (H2O) n (n = 2-5), were studied by using B3LYP density functional theory and MP2 ab initio methods along with the large basis sets (6-311 ++ G (d , p) and aug-cc-pVDZ). The equilibrium geometries, intermolecular binding energies, and anharmonic frequencies of the clusters are calculated and compared with those of pure water clusters and available experiments. SO2 tends to form cyclic hydrogen-bonded complexes with two or three water molecules. In the larger clusters, however, water molecules begin to retain the structure of pure water clusters and segregate from SO2. Infrared absorption assignments for the small clusters are discussed to resolve a possible incorrect assignment in a recent spectroscopic experiment on the clusters.