The effect of configuration interaction on the low terms of the spectra of oxygen

The ratios of the inter-multiplet separations for the lowest states of O, O + and O ++ obtained by Slater's method depart considerably from the observed values. In this method it is assumed that matrix elements of the Hamiltonian involving two different configurations are negligible, so that each state can be described by a single configuration, whereas these matrix elements are probably appreciable, and a better approximation is obtained by use of a wave function corresponding to a superposition of more than one configuration. The effect of this superposition of configurations has been called “configuration interaction”, and the general theory of it is discussed in Condon and Shortley's Theory of atomic spectra , Chap. xv. It is shown that it occurs only between terms of the same L and S , and of the same parity (∑ l even or odd). Few quantitative applications, however, have yet been made. A calculation by Bacher for Mg shows that the effect can be considerable although the states are quite widely separated.