Effects of solvation and core switching on the photoelectron angular distributions from (CO2)n(-) and (CO2)(n)(-).H2O

Photoelectron images are recorded in the photodetachment of two series of cluster anions, (CO(2))(n)(-), n=4-9 and (CO(2))(n)(-).H(2)O, n=2-7, with linearly polarized 400 nm light. The energetics of the observed photodetachment bands compare well with previous studies, showing evidence for switching between two anionic core structures: The CO(2)(-) monomer and covalent (CO(2))(2)(-) dimer anions. The systematic study of photoelectron angular distributions (PADs) sheds light on the electronic structure of the different core anions and indicates that solvation by several CO(2) molecules and/or one water molecule has only moderate effect on the excess-electron orbitals. The observed PAD character is reconciled with the symmetry properties of the parent molecular orbitals. The most intriguing result concerns the PADs showing remarkable similarities between the monomer and dimer anion cluster-core types. This observation is explained by treating the highest-occupied molecular orbital of the covalent dimer anion as a linear combination of two spatially separated monomeric orbitals.