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Global ab initio ground-state potential energy surface of N4.

We present a global ground-state potential energy surface for N4 suitable for treating high-energy vibrational-rotational energy transfer and collision-induced dissociation in N2-N2 collisions. To obtain the surface, complete active space second-order perturbation theory calculations were performed for the ground singlet state with an active space of 12 electrons in 12 orbitals and the maug-cc-pVTZ triple zeta basis set. About 17,000 ab initio data points have been calculated for the N4 system, distributed along nine series of N2 + N2 geometries and three series of N3 + N geometries. The six-dimensional ground-state potential energy surface is fitted using least-squares fits to the many-body component of the electronic energies based on permutationally invariant polynomials in bond order variables.