Identification of New Low-Lying Electronic States of the FeF Radical

Kermode, Stephen M.; Brown, John M.

doi:10.1006/jmsp.2002.8564

Cited by 6 publications

(5 citation statements)

References 32 publications

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“…Allen and Ziurys confirmed the ground state of FeF as 6 Δ i by pure rotational spectroscopy and obtained, among other parameters, an accurate bond distance r e = 1.7803 Å . Two more experimental works appeared more recently, where via fluorescence spectroscopy, Kermode and Brown probed the X 6 Δ and a limited number of excited states . Finally, the binding energy of FeF has been estimated to be D e = 107 ± 5 kcal/mol through high-temperature mass spectroscopy .…”

Section: Resultsmentioning

confidence: 99%

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Ab initio Study of the Diatomic Fluorides FeF, CoF, NiF, and CuF

Koukounas

Mavridis

2008

J. Phys. Chem. A

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The late-3d transition-metal diatomic fluorides MF = FeF, CoF, NiF, and CuF have been studied using variational multireference (MRCI) and coupled-cluster [RCCSD(T)] methods, combined with large to very large basis sets. We examined a total of 35 (2S+1)|Lambda| states, constructing as well 29 full potential energy curves through the MRCI method. All examined states are ionic, diabatically correlating to M(+)+F(-)((1)S). Notwithstanding the "eccentric" character of the 3d transition metals and the difficulties to accurately be described with all-electron ab initio methods, our results are, in general, in very good agreement with available experimental numbers.

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Section: Resultsmentioning

confidence: 99%

“…Finally, the binding energy of FeF has been estimated to be D e = 107 ± 5 kcal/mol through high-temperature mass spectroscopy . Relative experimental results from refs − will be contrasted with our own later on.…”

Section: Resultsmentioning

confidence: 99%

Ab initio Study of the Diatomic Fluorides FeF, CoF, NiF, and CuF

Koukounas

Mavridis

2008

J. Phys. Chem. A

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“…95͒ and experiment. 40 The ground state spin sextet states of iron fluoride [106][107][108] and the quartet states 91 have been characterized experimentally. The X 6 ⌬ and a 4 ⌬ states of FeF both have a valence electron configuration of ‫ء‬ 2 ␦ 3 .…”

Section: E Transition-metal Fluorides: the Hubbard U In Partially Iomentioning

confidence: 99%

Systematic study of first-row transition-metal diatomic molecules: A self-consistent DFT+U approach

Kulik

Marzari

2010

The Journal of Chemical Physics

113

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We present a systematic first-principles study of the equilibrium bond lengths, harmonic frequencies, dissociation energies, ground state symmetries, and spin state splittings of 22 diatomic molecules comprised of a first-row 3d transition-metal and a main-group element (H, C, N, O, or F). Diatomic molecules are building blocks of the key molecular bonding motifs in biological and inorganic catalytic systems, but, at the same time, their small size permits a thorough study by even the most computationally expensive quantum chemistry approaches. The results of several density-functional theory (DFT) approaches including hybrid, generalized-gradient, and generalized-gradient augmented with Hubbard U exchange-correlation functionals are presented. We compare these efficiently calculated DFT results with the highly accurate but computationally expensive post-Hartree-Fock approaches multireference configuration interaction (MRCI) and coupled cluster [CCSD(T)] as well as experimental values, where available. We show that by employing a Hubbard U approach, we systematically reduce average errors in state splittings and dissociation energies by a factor of 3. We are also able to reassign the ground state of four molecules improperly identified by hybrid or generalized-gradient approaches and provide correct assignment of all ground state symmetries as compared against experimental assignment and MRCI reference. By providing accuracy comparable to more expensive quantum chemistry approaches with the robust scaling of the generalized-gradient approximation, our DFT+U approach permits the study of very large scale systems with vastly improved results.

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“…Gas-phase reactions that are opposite to disproportionation of Fe(I) complexes to atomic Fe and iron(II) complexes are used for the generation of Fe(I) radicals. These reactions usually take place at high-temperatures (Knudsen cell experiments [2][3][4][5] ) and may involve other metal derivatives. Other ways of generating RFe involve reactions of atomic iron with hydrogen, halogen molecules or atoms, ammonia, etc.…”

Section: Introductionmentioning

confidence: 99%

“…8 Some RFe(I) complexes have been detected and characterized by spectroscopic methods. 5,7,[9][10][11][12][13][14][15][16][17] Quantum chemical calculations have been extensively used for the prediction of their electronic structure and spectroscopic properties. [18][19][20][21][22] This allowed the identifi cation of Fe(I) derivatives in astrophysical sources, such as in the atmosphere of stars and in sunspots.…”

Section: Introductionmentioning

confidence: 99%

The Generation of Neutral Derivatives of Low-Valence Iron, RFe(I), by Netralization—Reionization Mass Spectrometry

Zagorevski

2005

Eur J Mass Spectrom (Chichester)

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Neutralization-reionization mass spectrometry is applied for the generation of low-valence iron derivatives. Neutralization of Rfe(+) (R=H, F, Cl, Br, I, CN, OH, NH(2), acac, C(6)H(5)) ions resulted in the corresponding neutrals having lifetimes of at least 5 micros. Atom connectivities in RFe ions and neutrals were elucidated by a variety of tandem mass spectrometry techniques. The present study provides the first experimental evidence of the intrinsic stability of neutral IFe, NCFe, acacFe and C(6)H(5)Fe.

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Identification of New Low-Lying Electronic States of the FeF Radical

Cited by 6 publications

References 32 publications

Ab initio Study of the Diatomic Fluorides FeF, CoF, NiF, and CuF

Ab initio Study of the Diatomic Fluorides FeF, CoF, NiF, and CuF

Systematic study of first-row transition-metal diatomic molecules: A self-consistent DFT+U approach

The Generation of Neutral Derivatives of Low-Valence Iron, RFe(I), by Netralization—Reionization Mass Spectrometry

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