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

TL;DR

This study uses relativistic multi-reference configuration interaction calculations to determine the electronic states of IrO, identifying the ground state and low-lying excited states, and matching theoretical results with experimental data.

Contribution

The paper provides the first detailed relativistic CI calculations of IrO's electronic states, clarifying the ground state and low-lying states with experimental relevance.

Findings

Ground state is of 1/2 spin-orbit component, mixed with $^4\Sigma^-$ and $^2\Pi$ states.

Low-lying 5/2 and 7/2 states are nearly degenerate with the ground state.

Calculated bond length and vibrational frequency closely match experimental measurements.

Abstract

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 states for four spin-orbit components 1/2, 3/2, 5/2, and 7/2 are calculated intensively to clarify the ground state of IrO. Our calculation suggests that the ground state is of 1/2 spin-orbit component, which is highly mixed with $^4\Sigma^-$ and $^2\Pi$ states in $\Lambda-S$ notation. The two low-lying states of the 5/2 and 7/2 spin-orbit components are nearly degenerate with the ground state and locate only 234 and 260 cm$^{-1}$ above, respectively. The equilibrium bond length 1.712 \AA \ and harmonic vibrational frequency 903 cm$^{-1}$ of the 5/2 spin-orbit component are close to the experimental measurement of 1.724 \AA \ and 909 cm$^{-1}$, which suggests the 5/2 state should be the low-lying state contributed to spectra in experimental study. Moreover, the electronic states that give rise to the observed transition bands are assigned in terms of the excited energies and oscillator strengths obtained for the 5/2 and 7/2 spin-orbit components.