The electrostatic calculation of molecular energies - II. Approximate wave functions and the electrostatic method

Abstract The electrostatic method of calculating molecular energies introduced in the first paper of this series is investigated more closely. It is shown that, for wave functions obtained by a consistent application of the Ritz variational procedure (floating functions), the electrostatic method is equivalent to the conventional method in terms of the Hamiltonian integral. Such floating functions are used to investigate various electronic states of the hydrogen molecule and the hydrogen molecular ion, and to explain certain anomalies in previous calculations. A method for estimating charge densities in localized chemical bonds is outlined.