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Pure Appl. Chem., 2013, Vol. 85, No. 1, pp. 225-236

Published online 2012-07-23

Complexes of sulfuric acid with N,N‑dimethylformamide: An ab initio investigation

Liubov P. Safonova1,2*, Michail G. Kiselev1 and Irina V. Fedorova2

1 Institution of Russian Academy of Sciences, Institute of Solution Chemistry of the RAS, Akademicheskaya st.,1, Ivanovo, 153045 Russia
2 Ivanovo State University of Chemistry and Technology, Engels Pr., 7, Ivanovo, 153460 Russia

Abstract: The (H2SO4)2, H2SO4-DMF, and (H2SO4)2-DMF complexes have been investigated, using the B3LYP functional with cc-pVQZ basis set. The characteristics of structure and energetics for binary complexes of sulfuric acid with dimethylformamide (DMF) have been obtained for the first time. The H-bond formation both between molecules of sulfuric acid as well as sulfuric acid-DMF were studied, on the basis of Weinhold’s natural bond orbital (NBO) analysis. It was shown that the H-bond formation between sulfuric acid and DMF molecules is stronger than ones for the acids dimer. The value of charge transfer from lone pair (LP) orbitals of DMF oxygen to the antibonding orbital of acid OH-bond significantly exceeds the criterion of H-bond existance (0.01 e). As follows from energy, among the complexes under investigation the most preferable one was found to be (H2SO4)2-DMF in which sulfuric acid molecules are linked with each other by three H-bonds.