Affiliation:
1. Department of Chemistry, University of New Brunswick, PO Box 4400, Fredericton, NB E3B 5A3, Canada.
Abstract
Density functional theory (DFT) calculations were performed on the geometries and energies of CO31–/2–(CO2)nclusters with n = 1–5. For small clusters (n = 1 or 2), coupled cluster energies were obtained. Up to three CO2molecules are bound covalently to the dianion. Only weak electrostatic bonds were found in the monoanions. Calculated binding energies for the monoanions are in reasonable agreement with experimental values. The calculated adiabatic electron detachment energy for the dianion is –0.07 eV at n = 5, indicating that at least six CO2molecules will have to be added to CO32–before the dianionic cluster becomes, in the gas phase, more stable than the monoanionic one. In comparison, for sulfate – carbon dioxide clusters, stabilization occurs at n = 2. Carbonate clusters are compared with sulfate clusters for three solvent molecules: CO2, SO2, and H2O. Carbonate clusters have larger binding energies than sulfate clusters. For a given dianion, binding energies are largest for SO2and smallest for H2O. However, in all cases, stabilization of the carbonate dianion by clustering is more difficult to achieve than stabilization of the sulfate dianion.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
2 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献