The electronic states of KrF

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Abstract
Ab initio configuration interaction calculations for the electronic states of KrF are presented. States dissociating to Kr+F(2P), Kr+(2P)+F− and Kr* (3P)+F(2P) are investigated. Spin–orbit coupling is included in a semiempirical manner for the covalent and ionic states. The covalent curves are essentially repulsive in character, while the attractive ionic curves have wells 5.2–5.3 eV deep with calculated Re′s of 2.4–2.5 Å. The lowest 2Σ+ Rydberg state also forms a bound state with calculated values of Re=1.83 and De=1.33 eV. The intense laser emission at 248 nm is found to arise from the transition between the lowest ionic Ω=1/2 to covalent Ω=1/2 states (III1/2–I1/2 in our notation) calculated to occur at 241 nm with a spontaneous lifetime of 7 nsec. The observed emissions at 220 nm and 275 nm are assigned to the IV1/2–I1/2 and II3/2–I3/2 transitions, respectively.