Finite size scaling for critical parameters of simple diatomic molecules

We use the finite size scaling method to study the critical points, points of non-analyticity, of the ground state energy as a function of the coupling parameters in the Hamiltonian. In this approach, the finite size corresponds to the number of elements in a complete basis set used to expand the exact eigenfunction of a given molecular Hamiltonian. To illustrate this approach, we give detailed calculations for systems of one electron and two nuclear centres, Z ⁺ e ^?Z⁺. Within the Born-Oppenheimer approximation, there is no critical point, but without the approximation the system exhibits a critical point at Z = Z_c = 1.228279 when the nuclear charge, Z, varies. We show also that the dissociation occurs in a first-order phase transition and calculate the various related critical exponents. The possibility of generalizing this approach to larger molecular systems using Gaussian basis sets is discussed.