A study of FeCO⁺ with correlated wavefunctions

Abstract

A study of FeCO⁺ and Fe⁺ using both the second-order multi-configurational quasi-degenerate perturbation theory (MC-QDPT2) method and the coupled cluster theory with single and double replacements (augmented by perturbative triples) [CCSD(T)] method are presented. An all-electron triple-ζ valence plus polarization basis set was used in all calculations. The equilibrium CCSD(T) geometry of FeCO⁺ is found to be linear (⁴Σ^-) with a Fe⁺ to CO distance of 1.905 Å and a CO bond distance of 1.133 Å. The dissociation energy D₀ of ⁴Σ^- FeCO⁺ to ⁶D Fe⁺ and ¹Σ⁺ CO is predicted to be 28.8 kcal mol^-1, which is within the experimental range. Excited state properties including potential energy surfaces and D_e are predicted for the low lying sextet and quartet states of FeCO⁺. The first excited state is predicted to be ⁴Δ with a D_e of 17.6 kcal mol^-1. The lowest sextet state is predicted to be ⁶Δ with a D₀ of 12.3 kcal mol^-1. Several examples of pathological behavior at many levels of theory have been discovered and are discussed.

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