Structural, Electronic, and Magnetic Properties of Iron Disulfide FenS20/±(n= 1–6) Clusters

Tazibt, Slimane; Chikhaoui, A.; Bouarab, S.; Vega, A.

doi:10.1021/acs.jpca.7b00942

Cited by 6 publications

(4 citation statements)

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“…The Journal of Physical Chemistry A Article measured values. 45 Besides, the calculated bond lengths for CO (1.14 Å), NO (1.17 Å), and O 2 (1.22 Å) are also in very good agreement with their respective experimental values 46 1.13, 1.15, and 1.21 Å. Another relevant aspect is the treatment of exact exchange and the concomitant self-interaction correction for a right description of the structural and electronic properties and spin states.…”

Section: ■ Computational Methodssupporting

confidence: 73%

“…Benchmark calculations of bond length, vibrational frequency, VDE, adiabatic electron affinity (AEA), and ionization potential (IP) of Fe 2 0/± , S 2 0/± and FeS 0/± dimers showed a fairly good agreement between the calculated and the measured values. 45 Besides, the calculated bond lengths for CO (1.14 Å), NO (1.17 Å), and O 2 (1.22 Å) are also in very good agreement with their respective experimental values 46 1.13, 1.15, and 1.21 Å. Another relevant aspect is the treatment of exact exchange and the concomitant self-interaction correction for a right description of the structural and electronic properties and spin states.…”

Section: ■ Computational Methodssupporting

confidence: 73%

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Structural and Electronic Rearrangements in Fe₂S₂, Fe₃S₄, and Fe₄S₄ Atomic Clusters under the Attack of NO, CO, and O₂

Amitouche¹,

Saad²,

Tazibt³

et al. 2019

J. Phys. Chem. A

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We report results, based on density functional theory− generalized gradient approximation calculations, that shed light on how NO, CO, and O 2 interact with Fe 2 S 2 , Fe 3 S 4 , and Fe 4 S 4 clusters and how they modify their structural and electronic properties. The interest in these small iron sulfide clusters comes from the fact that they are at the protein cores and that elucidating fundamental aspects of their interaction with those light molecules which are known to modify their functionality may help in understanding complex behaviors in biological systems. CO and NO are found to bind molecularly, leading to moderate relaxations in the clusters, but nevertheless to changes in the spin-polarized electronic structure and related properties. In contrast, dissociative chemisorption of O 2 is much more stable than molecular adsorption, giving rise to significant structural distortions, particularly in Fe 4 S 4 that splits into two Fe 2 S 2 subclusters. As a consequence, oxygen tends to strongly reduce the spin polarization in Fe and to weaken the Fe−Fe interaction inducing antiparallel couplings that, in the case of Fe 4 S 4 , clearly arise from indirect Fe−Fe exchange coupling mediated by O. The three molecules (particularly CO) enhance the stability of the iron−sulfur clusters. This increase is noticeably more pronounced for Fe 2 S 2 than for the other iron−sulfur clusters of different compositions, a result that correlates with the fact that in recent experiments of CO reaction with Fe m S m (m = 1−4), the Fe 2 S 2 CO product results as a prominent one.

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Section: ■ Computational Methodssupporting

confidence: 73%

Section: ■ Computational Methodssupporting

confidence: 73%

Structural and Electronic Rearrangements in Fe₂S₂, Fe₃S₄, and Fe₄S₄ Atomic Clusters under the Attack of NO, CO, and O₂

Amitouche¹,

Saad²,

Tazibt³

et al. 2019

J. Phys. Chem. A

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“…Antiferromagnetic coupling between two pairs of iron atoms connected with monosulfur bridges was also observed , in the [Fe 4 S 4 X 4 ] 2– dianions. It was found recently that the magnetic coupling between iron atoms in dibridged [Fe 2 S 2 ] 0,± depends on charge; namely, the local spin magnetic moments of Fe are coupled ferromagnetically in the neutral and anion, but coupled antiferromagnetically in the cation. This behavior is similar to that found for the monobridged Fe 2 O series (see Figure ).…”

Section: Resultsmentioning

confidence: 99%

Dependence of Properties and Exchange Coupling Constants on the Charge in the Mn₂O_n and Fe₂O_n Series

et al. 2018

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The geometrical structure and properties of the neutral and singly charged MnO and FeO clusters ( q = 0, ±1) are computed using density functional theory with the generalized gradient approximation in the range 1 ≤ n ≤ 7. The geometrical structures and spin multiplicities of the corresponding species in all six series are similar except for a few exceptions. Antiferromagnetic coupling of total spin magnetic moments of the metal atoms in the lowest total energy states is observed for the majority of species in all six series when n = 1-5; correspondingly, the computed magnetic exchange coupling constants are mostly negative. The states of MnO and FeO are nonmagnetic or weakly ferromagnetic when n> 5 except for MnO where the ground state is antiferromagnetic. The computed adiabatic electron affinities and ionization energies of the neutral species in both series are quite close to one another and increase as n increases. However, the binding energies of a single oxygen atom and of an O dimer decrease as n increases and the MnO and FeO cations are barely stable with respect to the O abstraction. The most stable and least stable species at a given n are the anions and the cations, respectively. The electric dipole polarizability per atom decreases sharply when n moves from 1 to 4 and then remains nearly constant for larger n values in the anion series, whereas it is close to the asymptotic value already at n = 2 in the neutral series.

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“…In addition, the two methods are consistent in the description of the adiabatic electron affinity energy (AEA) and the vertical ionization potential (VDE). Tazibt et al [13] investigated the structure and magnetic properties of pure Fe clusters, on the basis of which the effect of doping with sulfur elements on the pure Fe cluster system was examined. e results show that the doping of sulfur with Fe enhances the binding energy of the atoms but has no significant effect on the magnetic properties of the system, implying that the magnetic properties of the iron-sulfur clusters are mainly dominated by the Fe atoms.…”

Section: Introductionmentioning

confidence: 99%

Interaction Study of Oxygen and Iron-Sulfur Clusters Based on the Density Functional Theory

Gao

Sui

et al. 2022

International Journal of Chemical Engineering

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For the petrochemical industry, the spontaneous burning of iron sulfide compounds has been a major issue. In this study, XRD characterization of samples of iron sulfide compounds with spontaneous combustion tendency revealed that amorphous FeS was the primary constituent of the samples. A molecular simulation was used to build an amorphous FeS cluster model, and the density functional theory was used to examine the adsorption and reactivity characteristics of Fe4S4 clusters with O2. Different adsorption structures are generated by considering different adsorption sites and the electronic characteristics of each adsorption structure are evaluated. The results show that O2 prefers to adsorb around Fe atoms and has repulsion with S atoms, and the adsorption energy is maximum when two O atoms are co-adsorbed around Fe atoms, which is 198.13 kJ/mol. After adsorption charge, oxygen is in the superoxide state. The calculation of the reaction path divides the reaction process into different stages and considers different reaction routes. A thorough evaluation of the energy barriers and reaction energies of the two exothermic reactions leads to the conclusion that reaction path 1 is the optimal reaction path, and the reaction can release a total of 582.76 kJ/mol of heat. According to calculations, dimeric sulfur S2 must absorb a large part amount of energy in order to conduct the oxidation process. However, because S2 is present in the Fe4S4 reaction system, it may start the oxidation reaction by absorbing heat from the system and releasing 470.94 kJ/mol of heat. As a result, we conclude that this spontaneous exothermic reaction is a major cause of iron sulfide compounds spontaneous combustion. The thermal oxidation of the dimeric sulfur S2 generated in the reaction system releases heat that aggregates with the heat from the Fe4S4 cluster’s oxidation reaction system, eventually causing spontaneous combustion as a result of the heat’s continual buildup. In this study, we explore the reason for the extremely easy oxidation and spontaneous burning of iron sulfide compounds from a microscopic perspective to provide a theoretical foundation for the prevention and control of iron sulfide compound spontaneous combustion in the petrochemical sector.

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Structural, Electronic, and Magnetic Properties of Iron Disulfide Fe_nS₂^0/±(n= 1–6) Clusters

Cited by 6 publications

References 98 publications

Structural and Electronic Rearrangements in Fe₂S₂, Fe₃S₄, and Fe₄S₄ Atomic Clusters under the Attack of NO, CO, and O₂

Structural and Electronic Rearrangements in Fe₂S₂, Fe₃S₄, and Fe₄S₄ Atomic Clusters under the Attack of NO, CO, and O₂

Dependence of Properties and Exchange Coupling Constants on the Charge in the Mn₂O_n and Fe₂O_n Series

Interaction Study of Oxygen and Iron-Sulfur Clusters Based on the Density Functional Theory

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Structural, Electronic, and Magnetic Properties of Iron Disulfide FenS20/±(n= 1–6) Clusters

Cited by 6 publications

References 98 publications

Structural and Electronic Rearrangements in Fe2S2, Fe3S4, and Fe4S4 Atomic Clusters under the Attack of NO, CO, and O2

Structural and Electronic Rearrangements in Fe2S2, Fe3S4, and Fe4S4 Atomic Clusters under the Attack of NO, CO, and O2

Dependence of Properties and Exchange Coupling Constants on the Charge in the Mn2On and Fe2On Series

Interaction Study of Oxygen and Iron-Sulfur Clusters Based on the Density Functional Theory

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Structural, Electronic, and Magnetic Properties of Iron Disulfide Fe_nS₂^0/±(n= 1–6) Clusters

Structural and Electronic Rearrangements in Fe₂S₂, Fe₃S₄, and Fe₄S₄ Atomic Clusters under the Attack of NO, CO, and O₂

Structural and Electronic Rearrangements in Fe₂S₂, Fe₃S₄, and Fe₄S₄ Atomic Clusters under the Attack of NO, CO, and O₂

Dependence of Properties and Exchange Coupling Constants on the Charge in the Mn₂O_n and Fe₂O_n Series