A comparison of ground‐ and excited‐state properties of [Ru(bz)2]2+ and bis(η6‐benzene)ruthenium(II) p‐toluenesulfonate using the density functional theory

The ground‐ and excited‐state properties of both [Ru(bz)2]2+ and crystalline bis(η6‐benzene)ruthenium(II) p‐toluenesulfonate are investigated using the density functional theory. A symmetry‐based technique is employed to calculate the energies of the multiplet structure splitting of the singly excited triplet states. For the crystalline system, a Buckingham potential is introduced to describe the intermolecular interactions between the [Ru(bz)2]2+ system and its first shell of neighbor molecules. The overall agreement between experimental and calculated ground‐ and excited‐state properties is good, as far as the absolute transition energies, the Stokes shift, and the geometry of the excited states are concerned. The calculated d‐d excitation energies of the isolated cluster are typically 1000–2000 cm−1 too low. An energy lowering is obtained in a1g→e1g(3E1g) excited state when the geometry of [Ru(bz)2]2+ is bent along the e1u Renner–Teller active coordinate. It vanishes as the crystal packing is taken into account. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1343–1353, 1999

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