EXTENSIVE AB INITIO STUDY OF THE OH+HCN REACTION - LOW LYING ELECTRONIC STATES OF THE STATIONARY POINTS ON THE (2)A' SURFACE

摘要

We found many stationary points (minima and transition states) for the title reaction on the (2)A' surface at unrestricted Hartree-Fock self-consistent field (UHF-SCF) level with two different basis sets. Stable adducts, as suggested by previous experimental works, have been ascertained and several reaction paths are obtained through intrinsic reaction coordinate (IRC) calculations. A link to the HNC+OH reaction is possible. Multiconfiguration SCF (MC-SCF) calculations have been carried out for the addition reaction with the lowest energy barrier in order to eliminate the spin contamination error on these geometries. Correlation energy at the stationary points was estimated via a perturbative scheme, Moller-Plesset at fourth order (MP4) which does not seem adequate for such a system, and via multireference double configuration interaction (MR-DCI) with extrapolation to full CI values for ground and first excited states. Electronic excitations may open some reaction channels. (C) 1996 American Institute of Physics. [References: 27]