Estimations of activation and enthalpies of reaction for HONO elimination from C2-C4 mononitroalkanes: A theoretical study

摘要

In recent paper we reported results concerning the gas phase enthalpies of formation of C1-C4 mononitroalkanes calculated using different multilevel and density functional theory (DFT)-based B3LYP techniques. The enthalpies of the C-N bond dissociation of these nitroalkanes had been also calculated. In present paper calculated activation enthalpies and enthalpies of reaction for HONO elimination from C2-C4 mononitroalkanes are represented. DFT/B3LYP, ab initio QCISD levels of theory together with G3, G3B3 G4 and CBS-QB3 were employed in this study. G4 calculated enthalpies of formation and reaction enthalpies of C-N bond rupture are performed in addition to activation and reaction enthalpies for HONO elimination. Comparison with available experimental activation energies showed that G3 and G3B3 estimations are of higher accuracy. The agreement of the CBS-QB3 calculations with experiment is also satisfactory. G4 calculated data demonstrated the worse agreement and did not produce correct trends for reaction enthalpies of C-N bond rupture.