Title

Taming the low-lying electronic states of FeH

Abstract

The low-lying electronic states (X 4Δ, A 4Π, a 6Δ, b 6Π) of the iron monohydride radical, which are especially troublesome for electronic structure theory, have been successfully described using a focal point analysis (FPA) approach that conjoined a correlation-consistent family of basis sets up to aug-cc-pwCV5Z-DK with high-order coupled cluster theory through hextuple (CCSDTQPH) excitations. Adiabatic excitation energies (T0) and spectroscopic constants (re, r0, Be, B0, D̄e, ωe, v0, αe, ωexe) were extrapolated to the valence complete basis set Douglas-Kroll (DK) aug-cc-pwCV∞Z-DK CCSDT level of theory, and additional treatments accounted for higher-order valence electron correlation, core correlation, spin-orbit coupling, and the diagonal Born-Oppenheimer correction. The purely ab initio FPA approach yields the following T0 results (in eV) for the lowest spin-orbit components of each electronic state: 0 (X 4Δ) < 0.132 (A 4Π) < 0.190 (a 6Δ) < 0.444 (b 6Π). The computed anharmonic fundamental vibrational frequencies (v0) for the 4,6Δ electronic states are within 3 cm-1 of experiment and provide reliable predictions for the 4,6Π states. With the cc-pVDZ basis set, even CCSDTQPH energies give an incorrect ground state of FeH, highlighting the importance of combining high-order electron correlation treatments with robust basis sets when studying transition-metal radicals. The FPA computations provide D0 = 1.86 eV (42.9 kcal mol-1) for the 0 K dissociation energy of FeH and ΔfH298° FeH(g) = 107.7 kcal mol-1 for the enthalpy of formation at room temperature. Despite sizable multireference character in the quartet states, high-order single-reference coupled cluster computations improve the spectroscopic parameters over previous multireference theoretical studies; for example, the X 4Δ → A 4Π and a 6Δ → b 6Π transition energies are reproduced to 0.012 and 0.002 eV, respectively, while the error for the problematic X 4Δ → a 6Δ intercombination excitation is reduced from at least 0.17 eV to about 0.04 eV. © 2012 American Institute of Physics.

Publication Title

Journal of Chemical Physics

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