【摘 要】
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The water-mediated neutral hydrolysis mechanisms of carbonyl sulfide(OCS)and carbon disulfide(CS2)has been re-examined by using the hybrid supramolecule/continuum models with n = 2-8 explicit water cl
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The water-mediated neutral hydrolysis mechanisms of carbonyl sulfide(OCS)and carbon disulfide(CS2)has been re-examined by using the hybrid supramolecule/continuum models with n = 2-8 explicit water cluster at the level of MP2(fc)(CPCM)/6-311++ G(d,p)//MP2(fc)(CPCM)/6-31+G(d).Our calculations indicate that the potential energy surfaces in water solution are different from the ones in the gas-phase,and only stepwise mechanism is observed in aqueous solution,i.e.,monothiocarbonic acid(H2CO2S)and dithiocarbonic acid(H2COS2)is formed via monothiocarbonate(OCSOH-)or dithiocarbonate(SCSOH-)and its counter-ion,protonated water cluster,(H2O)nH3O+.The predicted rate-determining step barriers for the stepwise mechanism in aqueous solution,about 90 kJ/mol(OCS)and 120 kJ/mol(CS2),show good agreement with the experimental values by using eight-water model including two cooperative water molecules.
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