Computed Potential Energy Surfaces for Chemical Reactions
The results of multireference singles and doubles CI calculations of potential energy surfaces for hydrogen atom addition to O2, N2, and NO and recombination of OH + O are discussed. The errors due to the use of externally contracted CI and due to the neglect of correlation of O 2s and N 2s electrons are analyzed. Similarities and differences between the surfaces for the addition reactions are discussed. The calculated HN2 addition surface is used in a simple dynamical treatment (one-dimensional tunneling through an Eckart barrier) to estimate the lifetime of the HN2 species. The OH + O recombination potential is found to exhibit complex features which require that electrostatic forces (dipole-quadrupole) and chemical forces be treated consistently.
KeywordsPotential Energy Surface Minimum Energy Path Atom Addition CASSCF Calculation Electron Result
Unable to display preview. Download preview PDF.
- 5.S.P. Walch, R.J. Duchovic, and C.M. Rohlfing, J. Chem. Phys. submitted.Google Scholar
- 7.S.P. Walch, C.M. Rohlfing, and C.F. Melius, J. Chem. Phys. to be published.Google Scholar
- 9.O. Nomura, S. Ikuta, and A. Iguwa, in “Applied Quantum Chemistry”, edited V.H. Smith, Jr., H.F. Schaefer III, and K. Morokuma (Reidel, 1984), p 243.Google Scholar
- 10.G.F. Adams and G.D. Bent, U.S. Army Ballistic Research Laboratory Technical Report (BRL-TR-2737), June 1986.Google Scholar
- 16.J. Almlöf, Molecule, a vectorized Gaussian integral program.Google Scholar
- 17.SWEDEN is a vectorized SCF-MCSCF-direct CI-conventional CI-CPF-MCPF program written by P.E.M. Siegbahn, C.W. Bauschlicher, Jr., B. Roos, P.R. Taylor, A. Heiberg, J. Almlöf, S.R. Langhoff, and D.P. Chong.Google Scholar