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Accurate ⁵⁷Fe Mossbauer Parameters from General Gaussian Basis Sets.

ABSTRACT: The prediction of isomer shifts in ⁵⁷Fe Mossbauer spectra is typically achieved by building calibration lines using the values of the density at the nuclear position. Using Slater-type orbital basis or large and specific Gaussian-type orbital basis has been thus far mandatory to achieve accurate predictions with density functional theory methods. In this work, we show that replacing the value of the density at the nucleus by the density integrated in a sphere of radius 0.06 au centered on the Fe nuclei yields excellent calibration lines (r² = 0.976) with a high predictive power (q² = 0.975, MAE = 0.055 mm·s^-1) while using the conventional def2-TZVP basis set and X-ray geometrical parameters. Our data set comprises 69 ⁵⁷Fe-containing compounds and 103 signals. We also find B3LYP performing significantly better than the PW91 functional.

SUBMITTER: Comas-Vila G

PROVIDER: S-EPMC8675134 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Accurate <sup>57</sup>Fe Mössbauer Parameters from General Gaussian Basis Sets.

Comas-Vilà Gerard G Salvador Pedro P

Journal of chemical theory and computation 20211122 12

The prediction of isomer shifts in <sup>57</sup>Fe Mossbauer spectra is typically achieved by building calibration lines using the values of the density at the nuclear position. Using Slater-type orbital basis or large and specific Gaussian-type orbital basis has been thus far mandatory to achieve accurate predictions with density functional theory methods. In this work, we show that replacing the value of the density at the nucleus by the density integrated in a sphere of radius 0.06 au centere ...[more]

PMID: 34806886

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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.

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Accurate ⁵⁷Fe Mossbauer Parameters from General Gaussian Basis Sets.

Publications

Accurate <sup>57</sup>Fe Mössbauer Parameters from General Gaussian Basis Sets.

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Dataset Information

Accurate 57Fe Mossbauer Parameters from General Gaussian Basis Sets.

Publications

Accurate <sup>57</sup>Fe Mössbauer Parameters from General Gaussian Basis Sets.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Accurate ⁵⁷Fe Mossbauer Parameters from General Gaussian Basis Sets.