Relativistic configuration interaction calculation on the ground and excited states of iridium monoxide.

We present the fully relativistic multi-reference configuration interaction calculations of the ground and low-lying excited electronic states of IrO for individual spin-orbit component. The lowest-lying state is calculated for Ω = 1/2, 3/2, 5/2, and 7/2 in order to clarify the ground state of IrO. Our calculation suggests that the ground state is of Ω = 1/2, which is highly mixed with (4)Σ(-) and (2)Π states in Λ - S notation. The two low-lying states 5/2 and 7/2 are nearly degenerate with the ground state and locate only 234 and 260 cm(-1) above, respectively. The equilibrium bond length 1.712 Å and the harmonic vibrational frequency 903 cm(-1) of the 5/2 state are close to the experimental measurement of 1.724 Å and 909 cm(-1), which suggests that the 5/2 state should be the low-lying state that contributes to the experimental spectra. Moreover, the electronic states that give rise to the observed transition bands are assigned for Ω = 5/2 and 7/2 in terms of the obtained excited energies and oscillator strengths.