Unified treatment of chemical and van der Waals forces via symmetry-adapted perturbation expansion

We propose a symmetry-adapted perturbation theory (SAPT) expansion of the intermolecular interaction energy which in a finite order provides the correct values of the constants determining the asymptotics of the interaction energy (the van der Waals constants) and is convergent when the energy of the interacting system is submerged in the continuum of Pauli-forbidden states-the situation common when at least one of the monomers has more than two electrons. These desirable features are achieved by splitting the intermolecular electron-nucleus attraction terms of the Hamiltonian into regular (long-range) and singular (short-range) parts. In the perturbation theory development, the regular part is treated as in the conventional polarization theory, which guarantees the correct asymptotics of the interaction energy, while the singular part is weakened sufficiently by an application of permutational symmetry projectors so that a convergent perturbation series is obtained. The convergence is demonstrated numerically, for both the chemical and van der Waals minima, by performing high-order calculations of the interaction energy of the ground-state lithium and hydrogen atoms-the simplest system for which the physical ground state is submerged in the Pauli-forbidden continuum. The obtained expansion enables a systematic extension of SAPT calculations beyond second order with respect to the intermolecular interaction operator.