Iron monocyanide (FeCN): Spin-orbit and vibronic interactions in low-lying electronic states

Abstract

The spin-orbit eigenvalues of low-energy quartet and sextet spatially degenerate electronic states of FeCN are reported, together with the combined effect of vibronic and spin-orbit interaction in the lowest-lying 14Δ and 16Δ states of FeCN, by using perturbational and variational method. Spin-orbit constants (ASO) have been calculated in the basis of: (a) two components of each degenerate state, (b) four components of 14Δ and 14Π (16Δ and 16Π) states, and (c) ten components of 16Δ, 16Π, 16Σ+, 14Δ, 14Π, and 14Σ+ states. The present calculations predict the values of ASO= −77 cm−1 for 16Δ and ASO= −108 cm−1 for 14Δ state in the lowest-energy spin-orbit manifolds of each state. The major perturbing state for the 14Δ state is the 14Π state (16Π for the sextet 16Δ). As expected, based on extremely small splitting and shallowness of the bending potential energy curves for the lowest-lying 4,6Δ states, the present study indicate that the vibronic coupling does not create significant splitting of the bending levels, but the influence of anharmonicity in the bending mode is more pronounced. However, the spin-orbit fine structure dominantly influences the spectra of this species.