How Many Water Molecules Are Actively Involved in the Neutral Hydration of Carbon Dioxide?
| Autor: | Minh Tho Nguyen, Greet Raspoet, Luc G. Vanquickenborne, Piet Th. Van Duijnen |
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| Rok vydání: | 1997 |
| Předmět: | |
| Zdroj: | The Journal of Physical Chemistry A. 101:7379-7388 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp9701045 |
| Popis: | The detailed reaction pathways for the hydration of carbon dioxide by water and water clusters containing two, three, and four water molecules (CO2 + nH2O → H2CO3 + (n − 1)H2O, n = 1−4) have been investigated in both gas phase and aqueous solution using ab initio molecular orbital (MO) theory up to the quadratic configuration interaction QCISD(T)/6-31G(d,p)//MP2/6-31G(d,p) level, both SCRF and PCM models of continuum theory, and a mixed approach based on MO calculations in conjunction with Monte Carlo and reaction field simulations. It is confirmed that the CO2 hydration constitutes a case of active solvent catalysis where solvent molecules actively participate as a catalyst in the chemical process. In aqueous solution the hydration mechanism is multimolecular, where geometric parameters of the solvent fully intervene in the reaction coordinate. The hydration reaction was found to proceed through an attack of a water oxygen to the CO2 carbon in concert with a proton transfer to a CO2 oxygen. The proton tr... |
| Databáze: | OpenAIRE |
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