| 초록 |
Lethal accidents caused by explosive reactions of toxic chemicals should be prevented and once happened, fast and safe control is of importance. An accurate understanding of thermodynamic properties and kinetic rates is the first step toward accomplishing the purpose. Using first principles density functional theory (DFT) we study hydrolysis reactions of two archetype chemicals, PCl3 and POCl3, to unveil potential energy surface over reaction coordinates. By calculating the intermediates and Gibbs free energy diagrams reaction mechanism and activation barriers. Our results indicate H2O molecules nearby the chemical species play a key role in catalyzing the hydrolysis reaction as a proton donor or acceptor. The catalytic mechanisms is explained as more water molecules attach the charge separation at the transition state is enhanced, leading to higher polarity and stabilization via hydrogen bonding network. It could dramatically reduce the activation energy of reactant complex. It is noteworthy that PCl3 react with H2O molecule by interplay of the proton transfer and dissociation of chlorine, while POCl3 first forms a penta-coordinated complex and then, quickly decomposes to HCl. |
