Perturbation theory of intermolecular interactions: What is the problem, are there solutions?

Abstract We review the nature of the problem in the framework of Rayleigh–Schrödinger perturbation theory (the polarization approximation) considering explicitly two examples: the interaction of two hydrogen atoms and the interaction of Li with H. We show, in agreement with the work of Claverie and of Morgan and Simon, that the LiH problem is dramatically different from the H 2 problem. In particular, the physical states of LiH are higher in energy than an infinite number of discrete, unphysical states and they are buried in a continuum of unbound, unphysical states, which starts well below the lowest physical state. Claverie has shown that the perturbation expansion, under these circumstances, is likely to converge to an unphysical state of lower energy than the physical ground state, if it converges at all. We review, also, the application of two classes of exchange perturbation theory to LiH and larger systems. We show that the spectra of three Eisenschitz–London ( EL ) class, exchange perturbation theories have no continuum of unphysical states overlaying the physical states and no discrete, unphysical states below the lowest physical state. In contrast, the spectra of two Hirschfelder–Silbey class theories differ hardly at all from that found with the polarization approximation. Not one of the EL class of perturbation theories, however, eliminates all of the discrete unphysical states. The best one establishes a one‐to‐one correspondence between the lowest energy states of the unperturbed and perturbed Hamiltonians, and a one‐to‐two correspondence for the higher states. We suggest that the EL class perturbation theories would be good starting points for the development of more effective perturbation theories for intermolecular interactions.