Electronic states of NaLi molecule: Benchmark results with Fock space coupled cluster approach.

Accurate potential energy curves (PECs) are obtained for 20 lowest lying electronic states of the NaLi molecule. The computational scheme used here is based on the multireference coupled cluster theory formulated in the (2,0) sector of the Fock space. The latter sector provides the description of states obtained by attachment of two electrons to the reference system. This makes it possible to adopt the doubly ionized NaLi+2 molecule as a Fermi vacuum. The latter has a very concrete advantage in calculations of the PECs since it dissociates into closed shell fragments (NaLi+2 → Na+ + Li+); hence, the restricted Hartree–Fock method can be used within the whole range of interatomic distances. Computed PECs and spectroscopic constants stay very close to the experimental values (if the latter are available) with the accuracy exceeding the other theoretical approaches including those based on the effective core polarization potentials. Relativistic corrections included at the infinite-order two-component level have a non-negligible effect on the accuracy of computed excitation and dissociation energies with contributions up to 50 cm−1. [ABSTRACT FROM AUTHOR]