Theoretical studies on anionic clusters of sulfate anions and carbon dioxide, SO 4 −1/−2 (CO2) n , n = 1−4
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Geometry optimizations were performed on monoanionic and dianionic clusters of sulfate anions with carbon dioxide, SO 4 −1/−2 (CO2) n , for n = 1–4, using the B3PW91 density functional method with the 6-311 + G(3df) basis set. Limited calculations were carried out with the CCSD(T) and MP2 methods. Binding energies, as well as adiabatic and vertical electron detachment energies, were calculated. No covalent bonding is seen for monoanionic clusters, with O3SO–CO2 bond distances between 2.8 and 3.0 Å. Dianionic clusters show covalent bonding of type [O3S–O–CO2]−2, [O3S–O–C(O)O–CO2]−2, and [O2C–O–S(O2)–O–CO2]−2, where one or two oxygens of SO 4 −2 are shared with CO2. Starting with n = 2, the dianionic clusters become adiabatically more stable than the corresponding monoanionic ones. Comparison with SO 4 −1/−2 (SO2) n and CO 3 −1/−2 (SO2) n clusters, the binding energies are smaller for the present SO 4 −1/−2 (CO2) n systems, while stabilization of the dianion occurs at n = 2 for both SO 4 −2 (CO2) n and SO 4 −2 (SO2) n , but only at n = 3 for CO 3 −2 (SO2) n .
KeywordsSulfate-carbon dioxide clusters Dianions Monoanions Dianion stabilization Electron detachment energies Covalent bonding in clusters Weakly bonded complexes Density functional methods Coupled cluster methods
The authors are indebted to Drs. Jack Passmore and Pablo Bruna for reading the manuscript and providing useful comments. Thanks to Robbie Weale for helping with the structures, and to Sonya Burrill for literature studies. Financial support provided by NSERC (Canada) is gratefully acknowledged. Excellent computing facilities have been made available through ACEnet.
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