Anomalous electron correlation due to near degeneracy effects: Low-lying ionic states of Ne and Ar

This Letter addresses a long-standing problem related to non-dynamical electron correlation effects. The origin of the large differential electronic correlation energy among the neutral 1S ground state, the lowest, 2P, ionic state and the first excited, 2S, ionic state of the Ne and Ar atoms is explained in terms of the near degeneracy of low-lying excited configurations. There is an anomalous correlation for the 2S state that is shown to be due to non-dynamical correlation involving a low-lying excited configuration. The conceptual framework used here is also appropriate to be used for other atomic and molecular systems.