Computational study of the reaction of N(2D) atoms with CH2F radicals:: An example of a barrier-free reaction involving very high internal energies -: art. no. 114312

The singlet potential-energy surface for the N(D-2)+CH2F((2)A(')) reaction has been studied employing both second-order Moller-Plesset and density-functional theories. The energies of the involved species have been refined using the Gaussian-2, complete basis set, and coupled-cluster singles and doubles (triples) methods. The reaction proceeds through the formation of an initial intermediate, which does not involve any activation barrier. Based on the energy profile for the singlet potential-energy surface, the preferred product should be the most exothermic one, namely, HCN+HF, followed by HNC+HF and FCN+H-2. This result seems in contradiction with a computational study of the kinetics of the title reaction in terms of the statistical theories, which leads to the prediction that the production of HNC+HF should be the dominant channel. Consequently, a limited molecular-dynamics study has been carried out, concluding that in fact the system behaves in a nonstatistical way. According to the molecular-dynamics study, the most exothermic channel, HCN+HF, should be the dominant one. An analysis of the possible role of the singlet surface in the reaction of N(S-4) with CH2F((2)A(')) has also been carried out. The computational study shows that the microcanonical coefficients for the nonadiabatic channels are much smaller than the competing adiabatic ones. Therefore, the reaction of N(S-4) with CH2F((2)A(')) should proceed on the triplet surface without spin change. (c) 2005 American Institute of Physics.