Quantum field theoretical methods in chemically bonded systems. V. Potential energy curves for N2(X1?g+) ? 2N (4S)

Abstract

Many-body perturbation theory is applied to the nitrogen triple bond for bond distances ranging from the atomic regime to about 0.6a0 shorter than equilibrium. A full-optimized reaction space model is used to compute orbital spaces with an even-tempered gaussian-type basis set and also with a nominal Bagus–Gilbert Slater-type basis set. Conservation of orbital angular momentum in the atomic regime leads to perturbative theory for Hartree–Fock plus proper dissociation. Angular momentum conservation can also be enforced with a scaled Slater–Condon parameter. Third-order dissociation energies and spectroscopic constants approach limits of the chosen basis sets. © 1993 John Wiley & Sons, Inc.