Configuration interaction study of the ground and excited states of TiO2 ring structures

Theoretical studies of the ground and lowest excited singlet and triplet states of a series of titanium dioxide ring structures, (TiO2)(2n), n = 3-9, are reported. Calculations are based on many-electron configuration theory, where energies of states and geometrical structures are determined by variational energy minimization. The lowest energy excited states correspond to excitations from oxygen 2p levels to unoccupied 3d orbitals on titanium. For each ring system, two types of excited state solutions are investigated: those that maintain periodic symmetry for individual orbitals and solutions that allow the symmetry to be broken. The latter solutions which correspond to localized states or excitons are found to be significantly lower in energy than the symmetric solutions. We compare the vertical excitation energy of these well-defined geometrical structures with size effects reported in experimental studies. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3564880]