Dataset Information

Mossbauer Spectroscopy of Iron Carbides: From Prediction to Experimental Confirmation.

ABSTRACT: The Mössbauer spectroscopy of iron carbides (?-Fe, ?'-FeC, ?-Fe2C, ?-Fe2C, ?-Fe5C2, h-Fe7C3, ?-Fe3C, o-Fe7C3, ?'-Fe4C, ?''-Fe4C, and ?'-Fe16C2) is predicted utilizing the all electron full-potential linearized augmented plane wave (FLAPW) approach across various functionals from LDA to GGA (PBE, PBEsol, and GGA?+?U) to meta-GGA to hybrid functionals. To validate the predicted MES from different functionals, the single-phase ?-Fe5C2 and ?-Fe3C are synthesized in experiment and their experimental MES under different temperature (from 13?K to 298?K) are determined. The result indicates that the GGA functional (especially, the PBEsol) shows remarkable success on the prediction of Mössbauer spectroscopy of ?-Fe, ?-Fe5C2 and ?-Fe3C with delocalized d electrons. From the reliable simulations, we propose a linear relationship between Bhf and ?B with a slope of 12.81?T/?B for iron carbide systems and that the proportionality constant may vary from structure to structure.

SUBMITTER: Liu XW

PROVIDER: S-EPMC4870625 | biostudies-literature | 2016 May

REPOSITORIES: biostudies-literature

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Mössbauer Spectroscopy of Iron Carbides: From Prediction to Experimental Confirmation.

Liu Xing-Wu XW Zhao Shu S Meng Yu Y Peng Qing Q Dearden Albert K AK Huo Chun-Fang CF Yang Yong Y Li Yong-Wang YW Wen Xiao-Dong XD

Scientific reports 20160518

The Mössbauer spectroscopy of iron carbides (α-Fe, γ'-FeC, η-Fe2C, ζ-Fe2C, χ-Fe5C2, h-Fe7C3, θ-Fe3C, o-Fe7C3, γ'-Fe4C, γ''-Fe4C, and α'-Fe16C2) is predicted utilizing the all electron full-potential linearized augmented plane wave (FLAPW) approach across various functionals from LDA to GGA (PBE, PBEsol, and GGA + U) to meta-GGA to hybrid functionals. To validate the predicted MES from different functionals, the single-phase χ-Fe5C2 and θ-Fe3C are synthesized in experiment and their experimental ...[more]

PMID: 27189083

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Project description:Imidazolate-containing {Fe(NO)(2)}(9) molecular squares have been synthesized by oxidative CO displacement from the reduced Fe(CO)(2)(NO)(2) precursor. The structures of complex 1 [(imidazole)Fe(NO)(2)](4), (Ford, Li, et al.; Chem. Commun.2005, 477-479), 2 [(2-isopropylimidazole)Fe(NO)(2)](4), and 3 [(benzimidazole)Fe(NO)(2)](4), as determined by X-ray diffraction analysis, find precise square planes of irons with imidazolates bridging the edges and nitrosyl ligands capping the irons at the corners. The orientation of the imidazolate ligands in each of the complexes results in variations of the overall structures, and molecular recognition features in the available cavities of 1 and 3. Computational studies show multiple low energy structural isomers and confirm that the isomers found in the crystallographic structures arise from intermolecular interactions. EPR and IR spectroscopic studies and electrochemical results suggest that the tetramers remain intact in solution in the presence of weakly coordinating (THF) and noncoordinating (CH(2)Cl(2)) solvents. Mössbauer spectroscopic data for a set of reference dinitrosyl iron complexes, reduced {Fe(NO)(2)}(10) compounds A ((NHC-iPr)(2)Fe(NO)(2)), and C ((NHC-iPr)(CO)Fe(NO)(2)), and oxidized {Fe(NO)(2)}(9) compounds B ([(NHC-iPr)(2)Fe(NO)(2)][BF(4)]), and D ((NHC-iPr)(SPh)Fe(NO)(2)) (NHC-iPr = 1,3-diisopropylimidazol-2-ylidene) demonstrate distinct differences of the isomer shifts and quadrupole splittings between the oxidized and reduced forms. The reduced compounds have smaller positive isomer shifts as compared to the oxidized compounds ascribed to the greater π-backbonding to the NO ligands. Mössbauer data for the tetrameric complexes 1-3 demonstrate larger isomer shifts, most comparable to compound D; all four complexes contain cationic {Fe(NO)(2)}(9) units bound to one anionic ligand and one neutral ligand. At room temperature, the paramagnetic, S = (1)/(2) per iron, centers are not coupled.

Project description:Six popular density functionals in conjunction with the conductor-like screening (COSMO) solvation model have been used to obtain linear Mössbauer isomer shift (IS) and quadrupole splitting (QS) parameters for a test set of 20 complexes (with 24 sites) comprised of nonheme nitrosyls (Fe-NO) and non-nitrosyl (Fe-S) complexes. For the first time in an IS analysis, the Fe electron density was calculated both directly at the nucleus, ρ(0)(N), which is the typical procedure, and on a small sphere surrounding the nucleus, ρ(0)(S), which is the new standard algorithm implemented in the ADF software package. We find that both methods yield (near) identical slopes from each linear regression analysis but are shifted with respect to ρ(0) along the x-axis. Therefore, the calculation of the Fe electron density with either method gives calibration fits with equal predictive value. Calibration parameters obtained from the complete test set for OLYP, OPBE, PW91, and BP86 yield correlation coefficients (r(2)) of approximately 0.90, indicating that the calibration fit is of good quality. However, fits obtained from B3LYP and B3LYP* with both Slater-type and Gaussian-type orbitals are generally found to be of poorer quality. For several of the complexes examined in this study, we find that B3LYP and B3LYP* give geometries that possess significantly larger deviations from the experimental structures than OLYP, OPBE, PW91 or BP86. This phenomenon is particularly true for the di- and tetranuclear Fe complexes examined in this study. Previous Mössbauer calibration fit studies using these functionals have usually included mononuclear Fe complexes alone, where these discrepancies are less pronounced. An examination of spin expectation values reveals B3LYP and B3LYP* approach the weak-coupling limit more closely than the GGA exchange-correlation functionals. The high degree of variability in our calculated S(2) values for the Fe-NO complexes highlights their challenging electronic structure. Significant improvements to the isomer shift calibrations are obtained for B3LYP and B3LYP* when geometries obtained with the OLYP functional are used. In addition, greatly improved performance of these functionals is found if the complete test set is grouped separately into Fe-NO and Fe-S complexes. Calibration fits including only Fe-NO complexes are found to be excellent, while those containing the non-nitrosyl Fe-S complexes alone are found to demonstrate less accurate correlations. Similar trends are also found with OLYP, OPBE, PW91, and BP86. Correlations between experimental and calculated QSs were also investigated. Generally, universal and separate Fe-NO and Fe-S fit parameters obtained to determine QSs are found to be of good to excellent quality for every density functional examined, especially if [Fe(4)(NO)(4)(μ(3)-S)(4)](-) is removed from the test set.

Dataset Information

Mossbauer Spectroscopy of Iron Carbides: From Prediction to Experimental Confirmation.

Publications

Mössbauer Spectroscopy of Iron Carbides: From Prediction to Experimental Confirmation.

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