Symmetry Assisted Consideration of the Dynamic Pseudo Jahn-Teller Problem in Mixed-Valence Species with Square Topology: Intervalence Optical Bands

摘要

Here we report the evaluation of the electronic and vibronic levels of mixed-valence tetra-ruthenium (2Ru(II) + 2Ru(III)) systems (assembled as two coupled Creutz-Taube complexes) for which possible molecular implementations of quantum-dot cellular automata was proposed. These complexes are representatives of Robin and Day classes I, II, and III and therefore the vibronic coupling is crucially important for the adequate description of the magnetic characteristics and profiles of the intervalence optical bands. We apply recently suggested symmetry-adapted approach to the accurate solution of the dynamic pseudo Jahn-Teller problems (~1B_(1g), 2~1A_(1g), ~1B_(2g), ~1E_u) (directX) (b_(1g) + e_u) and (~3A_(2g), ~3B_(1g), 2~3E_u) (directX) (b_(1g) + e_u) in bi-electronic mixed-valence species with square topology. The algorithm for the solution of the eigen-problem takes full advantage of the point symmetry arguments and therefore the full matrix of the Jahn-Teller JT Hamiltonian is blocked according to the irreps of the point group. The vibronic basis is used for the evaluation of the shape-functions of the intervalence optical absorption in mixed-valence tetra-ruthenium (2Ru(II) + 2Ru(III)) complexes.