TY - JOUR
T1 - Stability of XSO2 (X=F, Cl, and Br) radical
T2 - Impact of the basis set on X-S bonding energy in ab initio and DFT calculations
AU - Khalizov, Alexei F.
AU - Ariya, Parisa A.
N1 - Funding Information:
We acknowledge Natural Sciences and Engineering Research Council of Canada (NSERC), Le Fonds pour la Formation de Chercheurs et l'Aide à la Recherche (FCAR), Canadian Foundation for Innovation, and Environment Canada for financial support. A.F.K acknowledges NSERC/NATO for postdoctoral Science Fellowship. We are also grateful to the reviewer for helpful comments.
PY - 2001/12/14
Y1 - 2001/12/14
N2 - XSO2 is a labile intermediate, which can be formed upon pyrolysis of SO2X2 or upon interaction between halogen atom and sulphur dioxide in the troposphere. Detailed theoretical investigation demonstrated that even high correlated ab initio methods reproduce incorrectly BDE(X-SO2), unless very extended basis set is used. Thus, the bond energies derived previously using small basis sets may not be correct. At the same time, B3LYP with medium size basis sets produced results close to those obtained from Gaussian and CBS model chemistries. The source of discrepancies between ab initio and DFT methods is analysed and the implication of our results in the oxidation of tropospheric SO2 is discussed.
AB - XSO2 is a labile intermediate, which can be formed upon pyrolysis of SO2X2 or upon interaction between halogen atom and sulphur dioxide in the troposphere. Detailed theoretical investigation demonstrated that even high correlated ab initio methods reproduce incorrectly BDE(X-SO2), unless very extended basis set is used. Thus, the bond energies derived previously using small basis sets may not be correct. At the same time, B3LYP with medium size basis sets produced results close to those obtained from Gaussian and CBS model chemistries. The source of discrepancies between ab initio and DFT methods is analysed and the implication of our results in the oxidation of tropospheric SO2 is discussed.
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U2 - 10.1016/S0009-2614(01)01290-8
DO - 10.1016/S0009-2614(01)01290-8
M3 - Article
AN - SCOPUS:0042335818
SN - 0009-2614
VL - 350
SP - 173
EP - 180
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 1-2
ER -