Multireference configuration interaction calculations for positronium halides

Abstract

Multireference configuration interaction (MRCI) calculations of the positronium halides, PsF, PsCl, PsBr, and PsI, are carried out, to give positron ionization energies, positronium binding energies, and two-photon annihilation rates. All CI calculations consider only valence correlation effect with a frozen-core approximation, and use the orbitals with angular momentum up to 8. To incorporate the effects of many-body correlations in the energies and two-photon annihilation rates, the MRCI calculations are repeated with increasing reference configurations, and the full CI limits of these energies and annihilation rates are estimated. The contribution from orbitals having angular momentum greater than 8 to those values is also estimated. Relative to our previous single reference CI calculations, many-body correlation effects significantly increase the positron ionization energies, positronium binding energies, and two-photon annihilation rates. The structures of the positronium halides are also discussed.