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 th e hexaamminechromium(III) ion [Cr(NH3)(6)](3+) has been investigated t hrough density functional theory. The geometry of the (4)A(2g) ground state and of the T-4(2g) excited state are optimized. The latter is re laxed along an e(g) Jahn-Teller coordinate. The experimentally known g eometry distortion, i.e., an axial compression and an equatorial elong ation, together with the corresponding energy gain is well reproduced by our calculations. The results for the d-d excitation energies are i n reasonable agreement with experiment. The relative performance of lo cal and gradient-corrected functionals is discussed.