Extensive ab initio study of the OH+HCN reaction: Low lying electronic states of the stationary points on the 2A′ surface
- 22 September 1996
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 105 (12), 5091-5098
- https://doi.org/10.1063/1.472353
Abstract
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, Mo/ller–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.This publication has 18 references indexed in Scilit:
- Ab initio potential energy surfaces for unimolecular reactions during thermal conversion of acetyleneJournal of Molecular Structure: THEOCHEM, 1993
- Carbon-13 hyperfine constants of methyleneamidogen, hydroxymethyleneamidogen and aminooxomethyl radicalsThe Journal of Physical Chemistry, 1988
- Derivation of an extended geminal modelThe Journal of Chemical Physics, 1983
- Efficient diffuse function‐augmented basis sets for anion calculations. III. The 3‐21+G basis set for first‐row elements, Li–FJournal of Computational Chemistry, 1983
- Chemical model calculations of C2, C3, CH, CN, OH, and NH2 abundances in cometary comaeThe Astrophysical Journal, 1981
- The ground state of the CN+ ion: a multi-reference Ci studyChemical Physics Letters, 1980
- Molecular Applications of Coupled Cluster and Many-Body Perturbation MethodsPhysica Scripta, 1980
- Pressure dependence of the rate of reaction of OH with HCNChemical Physics Letters, 1978
- Applicability of the multi-reference double-excitation CI (MRD-CI) method to the calculation of electronic wavefunctions and comparison with related techniquesMolecular Physics, 1978
- Note on an Approximation Treatment for Many-Electron SystemsPhysical Review B, 1934