Ab initio potential energy surfaces for NH(Σ3−)–NH(Σ3−) with analytical long range

Abstract

We present four-dimensional ab initio potential energy surfaces for the three different spin states of the NH(Σ3−)–NH(Σ3−) complex. The potentials are partially based on the work of Dhont et al. [J. Chem. Phys. 123, 184302 (2005)]. The surface for the quintet state is obtained at the RCCSD(T)/augmented correlation-consistent polarized valence triple-zeta (aug-cc-pVTZ) level of theory and the energy differences with the singlet and triplet states are calculated at the complete active space with nth-order perturbation theory/aug-cc-pVTZ (n=2,3) level of theory. The ab initio potentials are fitted to coupled spherical harmonics in the angular coordinates, and the long range is further expanded as a power series in 1/R. The RCCSD(T) potential is corrected for a size-consistency error of about 0.5×10−6 Eh prior to fitting. The long-range coefficients obtained from the fit are found to be in good agreement with first and second-order perturbation theory calculations.