Role of the electric dipole moment in positron binding to the ground and excited states of the BeO molecule

摘要

Self-consistent-field and multireference single- and double-excitation configuration interaction (CI) calculations have been carried out for various electronic states of the beryllium oxide molecule and their positron-attached counterparts. Particular emphasis is placed on the correlation between the polarity of a given BeO state and the magnitude of the positron binding energy as the internuclear distance is varied. Potential curves are computed for all BeO states that correlate with the first three atomic limits for this system and good agreement is found between the experimental and calculated spectroscopic constants in all cases. The present level of CI treatment is known to underestimate the positron affinities of atoms by at least several tenths of an eV, and this fact needs to be taken into account in evaluating the results for positron binding to molecules. The lowest BeO excited states ((3,1)Pi) are not found to bind with a positron in the Franck-Condon region due to their comparatively small dipole moments caused by O to Be charge transfer relative to the X (1)Sigma(+) ground state, which in turn does have a fairly sizeable positron affinity. The situation changes significantly as dissociation proceeds, however, with both (4,2)Pi and (2)Sigma(+) positronic states lying several tenths of an eV lower than their neutral counterparts over a broad range of internuclear distance.