Spin splittings from first-order symmetry-adapted perturbation theory without single-exchange approximation

The recently proposed spin-flip symmetry-adapted perturbation theory (SF-SAPT) first-order exchange energy [Patkowski et al., J. Chem. Phys. 148, 164110 (2018)] enables the standard open-shell SAPT approach to treat arbitrary spin states of the weakly interacting complex. Here, we further extend first-order SF-SAPT beyond the single-exchange approximation to a complete treatment of the exchanges of electrons between monomers. This new form of the exchange correction replaces the single-exchange approximation with a more moderate single-spin-flip approximation. The newly developed expressions are applied to a number of small test systems to elucidate the quality of both approximations. They are also applied to the singlet-triplet splittings in pancake bonded dimers. The accuracy of the single-exchange approximation deteriorates at short intermolecular separations, especially for systems with few electrons and for the high-spin state of the complex. In contrast, the single-spin-flip approximation is exact f...