Structural and spectroscopic study of the excited electronic states of silver dihalides by quantum chemical methods

Abstract

The structural and electronic properties of the excited electronic states of AgX₂ (X = F, Cl, Br, and I), have been calculated, taking electron correlation and spin–orbit coupling into account and employing improved relativistic-effective-core potentials for silver and the halogen atoms. The relative ordering of the excited states of these molecules has been discussed via molecular-orbital arguments. The spin–orbit splittings of three degenerate electronic states (²Π_g, ²Π_u, and ²Δ_g) have been calculated and the spin–orbit induced inter-state (Σ − Π) coupling has been discussed. The composition of the spin–orbit eigenstates is analyzed in terms of scalar-relativistic electronic states. Finally, a theoretical prediction of the photodetachment bands of the title molecules has been accomplished.