Ground State and Excited Stated Properties of Hexaamminechromium(III) Ion: A Density Functional Study

The electronic structure of the ground and lowest excited states of the hexaamminechromium(III) ion [Cr(NH(3))(6)](3+) has been investigated through density functional theory. The geometry of the (4)A(2g) ground state and of the (4)T(2g) excited state are optimized. The latter is relaxed along an e(g) Jahn-Teller coordinate. The experimentally known geometry distortion, i.e., an axial compression and an equatorial elongation, together with the corresponding energy gain is well reproduced by our calculations. The results for the d-d excitation energies are in reasonable agreement with experiment. The relative performance of local and gradient-corrected functionals is discussed.