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Issue 1, 2006
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Computational study of the energetics of 3Fe(CO)4, 1Fe(CO)4 and 1Fe(CO)4(L), L = Xe, CH4, H2 and CO

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Abstract

Large basis CCSD(T) calculations are used to calculate the energetics of 3Fe(CO)4, 1Fe(CO)4 and 1Fe(CO)4(L), L = Xe, CH4, H2 and CO. The relative energy of the excited singlet state of Fe(CO)4 with respect to the ground triplet state is not known experimentally, and various lower levels of theory predict very different results. Upon extrapolating to the infinite basis set limit, and including corrections for core–core and core–valence correlation, scalar relativity, and multi-reference character of the wavefunction, the best CCSD(T) estimate for the spin-state splitting in iron tetracarbonyl is 2 kcal mol−1. Calculation of the dissociation energy of 1Fe(CO)4(L) into singlet fragments, taken together with known experimental behaviour of triplet Fe(CO)4, provides independent evidence for the fact that the spin-state splitting is smaller than 3 kcal mol−1. These calculations highlight some of the challenges involved in benchmark calculations on transition metal containing systems.

Graphical abstract: Computational study of the energetics of 3Fe(CO)4, 1Fe(CO)4 and 1Fe(CO)4(L), L = Xe, CH4, H2 and CO

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Publication details

The article was received on 20 Sep 2005, accepted on 17 Oct 2005 and first published on 01 Nov 2005


Article type: Paper
DOI: 10.1039/B513325D
Citation: Phys. Chem. Chem. Phys., 2006,8, 93-100
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    Computational study of the energetics of 3Fe(CO)4, 1Fe(CO)4 and 1Fe(CO)4(L), L = Xe, CH4, H2 and CO

    J. Carreón-Macedo and J. N. Harvey, Phys. Chem. Chem. Phys., 2006, 8, 93
    DOI: 10.1039/B513325D

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