The excited states of Zn2 and Zn3. Inclusion of the correlation effects

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Abstract
This paper deals with the electronic structure of the Zn2 and Zn3 clusters. Independent a b i n i t i o SCF calculations are performed for the ground and excited states of Zn2, and the SCF MOs are determined for respective states. By using these MOs, CI calculations taking account of the correlation effects among 4s‐ and 4p‐like electrons are carried out. This is an improvement over previous CI calculations, which used the occupied and virtual (or improved virtual) MOs computed for the ground state, and thus disregarded the reorganization effect. The calculated excitation energies for Zn2 are 0.8–1.3 eV smaller than experiment. The inclusion of the correlation between the inner (3d‐like) and valence (4s‐ and 4p‐like) shells ameliorates the result only slightly (by 0.03–0.05 eV). The remaining discrepancy is attributed to relatively poor description of the ground state as compared with that of the excited states. Similar calculations are performed for the electronic structure of Zn3. Calculated excitation energies are compared with the absorption spectra of Zn aggregates (size unknown) in an argon matrix.