Ionic dissociations of chlorosulfonic acid in microsolvated clusters: A density functional theory and ab initio MO study

• 来源期刊: 中国科学B辑（英文版）
• 年，卷（期）: 2008,（4）
• 页码范围: 305-315
• 页数: 11页
• 语种: 英文
• DOI: 10.1007/s 11426-007-0106-9

摘要

lonic dissociation of chlorosulfonic acid (HSO3Cl) in the molecular clusters HSO3Cl-(H2O)n (n=1-4) and HSO3Cl-NH3-(H2O)n (n=0-3) was investigated by density functional theory and ab initio molecular orbital theory. The equilibrium structures, binding energies, and thermodynamic properties, such as relative enthalpy and relative Gibbs free energy, and were calculated using the hybrid density func-tional (B3LYP) method and the second order Moller-Plesset approximation (MP2) method with the 6-311++G** basis set. Chlorosulfonic acid was found to require a minimum of three water molecules for ionization to occur and at least one water molecule to protonate ammonia. The corresponding clusters with fewer water molecules were found to be strongly hydrogen-bonded. The related properties and acid strength of chlorosulfonic acid were discussed and compared to the acid strengths of perchloric acid and sulfuric acid in the context of clusters with ammonia and water. The relative stabilities of these clusters were also investigated.