Reactions of ROH (R=H, CH₃) with HNCO: A theoretical study

Abstract

Density functional calculations have been performed to investigate the reactions of ROH (R=H, CH₃) with HNCO. Four-centered transition states have been predicted for both the reactions. Both the reactions are predicted to be exothermic in nature. Inclusion of electron correlation decreases the exothermicity only by a small amount. However, the energy of activation decreases significantly with the inclusion of electron correlation. Analysis of electronic charge density values at the bond critical points of the four-membered transition states predicts the C-O bond to be non-covalent while all other bonds are predicted to be covalent. Second-order Moller-Plesset perturbation (MP2) calculations have also been made for the reactants, transition states and the products. Results of density functional calculations are in excellent agreement with those obtained from MP2 studies.