DFT Functionals for Modeling of Polyethylene Chains Cross-Linked by Metal Atoms. DLPNO–CCSD(T) Benchmark Calculations

Blaško, Martin; Pašteka, Lukáš F.; Urban, Miroslav

doi:10.1021/acs.jpca.1c04793

Cited by 11 publications

(6 citation statements)

References 123 publications

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“…For this, we confirmed the use of DLPNO–CCSD(T)/def2-TZVP − calculations as an appropriate post-Hartree–Fock benchmark for Nd cation/molecule interactions, specifically based on the Nd–H + complex, due to the availability of high-resolution data for comparison . This level of theory was chosen to ensure that it was practical for use on our largest benchmark system.…”

Section: Computational Detailsmentioning

confidence: 79%

Exploring Coordination of Neodymium in Ionic Liquid: Insights to Guide Sustainable Recovery

Dobhal,

Pham,

Tawfik

et al. 2023

ACS Sustainable Chem. Eng.

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Neodymium is a critical metal essential for advancing sustainable clean energy technologies, as it is a crucial component in the manufacturing of NdFeB permanent magnets, part of wind turbines, electric vehicles, and advanced electronics. Its recovery from secondary sources using electrochemical deposition in ionic liquids has the potential to sustainably achieve a closed-loop alternative to obtain the metal. The presence of water in low, specific concentrations in ionic liquid has been previously shown to catalyze electrodeposition of Nd with amplified current densities and easier reduction of Nd3+, but the structure(s) of the metal/mixed-ligand species that led to this amplification was previously only hypothesized. Stringently benchmarked quantum chemical calculations reveal a complex potential energy landscape that underpins the structural transformations arising from the introduction of water into the coordination sphere of Nd3+ surrounded by bis(trifluoromethanesulfonyl)imide (TFSI) anions. Three distinct changes were observed in the Nd3+-TFSI– complexes upon addition of water: (i) cis/trans transformation of TFSI, (ii) transition from bidentate to monodentate TFSI– coordination, and (iii) displacement of TFSI– ligands by water. Energetic analyses of these structural changes can explain experimentally observed water-loading effects regarding the ease of electrochemical reduction of Nd3+ and its deposition. These outcomes provide a platform for tuning ionic liquid media compositions to enhance rare-earth metal recovery.

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Section: Computational Detailsmentioning

confidence: 79%

Exploring Coordination of Neodymium in Ionic Liquid: Insights to Guide Sustainable Recovery

Dobhal,

Pham,

Tawfik

et al. 2023

ACS Sustainable Chem. Eng.

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“… 106 The original MOBH35 107 , 108 set is also included to provide comparability to prior works. Binding energies of metal-linked alkyl chains are assessed on the MLA24 109 benchmark set. The results are depicted in Figures 9 and 14 .…”

Section: Resultsmentioning

confidence: 99%

Optimization of the r²SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

et al. 2022

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The “Swiss army knife” composite density functional electronic-structure method r 2 SCAN-3c ( J. Chem. Phys. 2021 , 154 , 064103) is extended and optimized for the use with Slater-type orbital basis sets. The meta generalized-gradient approximation (meta-GGA) functional r 2 SCAN by Furness et al. is combined with a tailor-made polarized triple-ζ Slater-type atomic orbital (STO) basis set (mTZ2P), the semiclassical London dispersion correction (D4), and a geometrical counterpoise (gCP) correction. Relativistic effects are treated explicitly with the scalar-relativistic zeroth-order regular approximation (SR-ZORA). The performance of the new implementation is assessed on eight geometry and 74 energy benchmark sets, including the extensive GMTKN55 database as well as recent sets such as ROST61 and IONPI19. In geometry optimizations, the STO-based r 2 SCAN-3c is either on par with or more accurate than the hybrid density functional approximation M06-2X-D3(0)/TZP. In energy calculations, the overall accuracy is similar to the original implementation of r 2 SCAN-3c with Gaussian-type atomic orbitals (GTO), but basic properties, intermolecular noncovalent interactions, and barrier heights are better described with the STO approach, resulting in a lower weighted mean absolute deviation (WTMAD-2(STO) = 7.15 vs 7.50 kcal mol –1 with the original method) for the GMTKN55 database. The STO-optimized r 2 SCAN-3c outperforms many conventional hybrid/QZ approaches in most common applications at a fraction of their cost. The reliable, robust, and accurate r 2 SCAN-3c implementation with STOs is a promising alternative to the original implementation with GTOs and can be generally used for a broad field of quantum chemical problems.

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“…(“TightSCF” keyword), and the DFT integration grid was increased by applying the ORCA keywords “Grid4” and “Finalgrid5” (for ORCA version 4.2.1). The DLPNO–CCSD(T) method − was used together with basis set extrapolations at the triple-ζ/quadruple-ζ levels to derive high-accuracy energies at the complete basis set (CBS) limit, see the Supporting Information (SI) for details. The RIJK approximation was used to speed up the HF step in the DLPNO–CCSD(T) calculations, while RI-J and RIJCOSX were used for nonhybrid and hybrid DFT methods, respectively.…”

Section: Methodsmentioning

confidence: 99%

Mechanistic Aspects of Rhodium-Catalyzed Isoprene Hydroformylation: A Computational Study

Köhnke,

Bjornsson,

Leitner

et al. 2024

Organometallics

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The hydroformylation of conjugated dienes is a highly interesting reaction, giving access to bifunctional aldehyde products. However, due to low activity, caused by the formation of stable η 3 -allylic intermediates, it has received much less academic attention, both experimentally and theoretically, than classical monoalkene hydroformylation. We herein present a comprehensive computational mechanistic study of the hydroformylation of isoprene as the simplest example of an asymmetrically substituted conjugated diene, via a Rh/dppe catalyst. A benchmarking study assessing the accuracy of Rh complex structures and energies with various methods was carried out, from which a protocol combining dispersion-corrected density functional theory (DFT) for geometries and vibrational corrections and DLPNO−CCSD(T) for reaction energies was derived. The predicted reaction mechanism of isoprene hydroformylation leading to the formation of 3methyl-3-pentenal is derived from the classic Wilkinson cycle for monoene hydroformylation with a few deviations. Among them is the prediction of a η 3 /η 3 -allylic rearrangement following a Berry pseudorotation mechanism that has rarely been discussed in the literature. The prediction of the relevant intermediates and transition states is highly sensitive to the computational protocol, with the implicit solvation model introducing the greatest uncertainty. A TOF of 47 h −1 was predicted to be in good agreement with experimental results. An investigation of subsequent product isomerization revealed a high hydrogen transfer barrier, making the isomerization via β-hydride elimination unfavorable.

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DFT Functionals for Modeling of Polyethylene Chains Cross-Linked by Metal Atoms. DLPNO–CCSD(T) Benchmark Calculations

Cited by 11 publications

References 123 publications

Exploring Coordination of Neodymium in Ionic Liquid: Insights to Guide Sustainable Recovery

Exploring Coordination of Neodymium in Ionic Liquid: Insights to Guide Sustainable Recovery

Optimization of the r²SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

Mechanistic Aspects of Rhodium-Catalyzed Isoprene Hydroformylation: A Computational Study

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DFT Functionals for Modeling of Polyethylene Chains Cross-Linked by Metal Atoms. DLPNO–CCSD(T) Benchmark Calculations

Cited by 11 publications

References 123 publications

Exploring Coordination of Neodymium in Ionic Liquid: Insights to Guide Sustainable Recovery

Exploring Coordination of Neodymium in Ionic Liquid: Insights to Guide Sustainable Recovery

Optimization of the r2SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

Mechanistic Aspects of Rhodium-Catalyzed Isoprene Hydroformylation: A Computational Study

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Product

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Optimization of the r²SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets