Dynamic correlation hydrogen abstraction

ABSTRACT. The results of multireference singles and doubles Cl calculations of potential energy surfaces for hydrogen atom addition to O2, N2, and NO and recombination of OH -h O are discussed. The errors due to the use of externally contracted Cl 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 -h O recombination potential is found to exhibit complex features which require that electrostatic forces (dipole-quadrupole) and chemical forces be treated consistently. 

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