Performance of Density Functional Theory and Relativistic Effective Core Potential for Ru-Based Organometallic Complexes

Abstract

Herein a performance assessment of density functionals used for calculating the structural and energetic parameters of bi- and trimetallic Ru-containing organometallic complexes has been performed. The performance of four popular relativistic effective core potentials (RECPs) has also been assessed. On the basis of the calculated results, the MN12-SX (range-separated hybrid functional) demonstrates good performance for calculating the molecular structures, while MN12-L (local functional) performs well for calculating the energetics, including that of the Ru-Ru bond breaking process. The choice of appropriate density functional is a crucial factor for calculating the energetics. The LANL08 demonstrates the lowest performance of the RECPs for calculating the molecular structures, especially the Ru-Ru bond length.

Hydride Pinning Pathway in the Hydrogenation of CO2 to Formic Acid on Dimeric Tin Dioxide

“…The best outcome of the initial analysis is the range‐separated hybrid meta‐NGA (non‐separable gradient approximation) MN12‐SX functional in describing bond dissociation enthalpies of the bonds close to experimental data. The accuracy of MN12‐SX functional agrees with previous studies in predicting both structures and energies ,. Along with it, the def2TZVPP basis set proves very good in minimizing the basis set superposition error (BSSE), giving errors of <0.04 eV, thus providing results close to the DFT basis set limit .…”

“…The accuracy of MN12-SX functional agrees with previous studies in predicting both structures and energies. [44,45] Along with it, the def2TZVPP basis set proves very good in minimizing the basis set superposition error (BSSE), giving errors of < 0.04 eV, thus providing results close to the DFT basis set limit. [42] Therefore, for geometry relaxation and frequency calculation, we have used MN12-SX/def2TZVPP level employing ultrafine integration grid.…”

Density functional theory computational study of [M∙Pro‐H]+ (M = Pb, Ba, or Pt) complexes in the gas phase

“…The two density functional methods were employed owing to their accurate predictions for metal‐ligand binding energies, structure energies, proton affinities, and harmonic frequencies, and for improved treatment of spin states, and have a smaller mean absolute deviation or mean unassigned error than the more widely used B3LYP method [16,19]; it has been shown [20] that M06‐L and X3LYP, when used with a correlation consistent basis set, reproduce metal ion‐organic ligand structural parameters to within about 0.01 Å deviation from measured values. For this reason, aug‐cc‐pVDZ [21] was used for H, N, C, and O, and SDDAll [22] with effective core potentials was used for the metals to accurately describe the heavy elements [23]. [ M ·Pro‐H] + multiplicities of singlet, triplet, and quintet were explored for both isomer types as they can affect ordering of structural energies [2].…”

Magneto-Refractive Effect and Mechanism Analysis of Erbium-Ytterbium Co-Doped Silica Fiber

“…Here, we used a relativistic effective core potential (RECP) to account for relativistic effects [18]. The B3LYP method of DFT was used to optimize the model of the Er/Yb co-doped silica three-ring fiber materials.…”