Density functional theory analysis of carbonyl sulfide hydrolysis: effect of solvation and nucleophile variation

作者：Zhang Ri Guang; Ling Li Xia; Wang Bao Jun^*

来源：Journal of Molecular Modeling, 2012, 18(4): 1255-1262.

DOI：10.1007/s00894-011-1155-8

• Carbonyl sulfide
• Hydrolysis
• OH-
• H2O
• Thermodynamics
• Kinetics
• Density functional theory

The detailed mechanisms of the hydrolysis of carbonyl sulfide (OCS) by nucleophilic water and hydroxide ion in both the gas phase and bulk water solvent have been investigated using density functional theory. Various reaction channels on the potential surface have been identified. The thermodynamic results demonstrate that the hydrolysis of OCS by nucleophilic water and hydroxide ion should proceed more favorably at low temperature. The hydrolysis of OCS by the hydroxide ion is the main reaction channel from thermodynamic and kinetic perspectives, and the bulk solvent can influence the rate-determining step in this channel. However, the solvent barely modifies the activation energy of the rate-determining step. For the hydrolysis of OCS by nucleophilic water, the solvent does not modify the rate-determining step, and the corresponding activation energy of the rate-determining step barely changes. This bulk solvent effect suggests that most of the contribution of the solvent is accounted for by considering one water molecule and a hydroxide ion.

• 出版日期2012-4
• 单位太原理工大学