@Article{JComputChem_20_1343, author = {F. Gilardoni and J. Weber and A. Hauser and C. Daul}, title = {{A comparison of ground- and excited-state properties of [Ru(bz)$_2$]$^{2+}$ and bis($\eta^{6}$-benzene)ruthenium(II)p-toluenesulfonate using density functional theory}}, journal= {J. Comput. Chem.}, ISSN = {0192-8651}, volume= {20}, number= {13}, pages = {1343-1353}, url = {http://www3.interscience.wiley.com/cgi-bin/abstract/63500754/START}, doi= {10.1002/(SICI)1096-987X(199910)20:133.0.CO;2-U}, keywords= {quantum chemical calculations;photophysical properties;multiplet structure;intermolecular interactions;Jahn-Teller distortion}, abstract = {{The ground- and excited-state properties of both [Ru(bz)$_2$]$^{2+}$ and crystalline bis($\eta^{6}$-benzene)ruthenium(II) {\em 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 {\em d}-{\em d} excitation energies of the isolated cluster are typically 1000-2000 cm$^{-1}$ too low. An energy lowering is obtained in {\em a}$_{1{\em g}}$ → {\em e}$_{1{\em g}}$($^{3}${\em E}$_{1{\em g}}$) excited state when the geometry of [Ru(bz)$_{2}$]$^{2+}$ is bent along the {\em e}$_{1{\em u}}$ Renner-Teller active coordinate. It vanishes as the crystal packing is taken into account.}}, year = {1999} }