The electronic structures of CrO42-, CrO3X-, and CrO2X2with X = F and Cl are compared by using the SCF Xα-SW method. Results are presented for the ground state and for the lower lying singlet and triplet excitations. The lowest energy excited states are calculated to arise from the promotions lt1→ 2e in CrO42-, la2→ 9e in CrO3F-, la2→10e in CrO3Cl-, 7b2→ 14a1in CrO2F2, and 8b2→ 17a, in CrO2Cl2. The predicted energies and symmetries of the lowest lying excited states and their very small singlet-triplet splittings are in satisfactory agreement with the available experimental data for the halogen-substituted systems. Relativistic calculations for the ground state of CrO42-suggest that spin-orbit interactions are not important for a qualitative description of the lower excited states.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Inorganic Chemistry