Assessment of Tuned Range Separated Exchange Functionals for Spectroscopies and Properties of Uranium Complexes

Duignan, Thomas J.; Autschbach, Jochen; Batista, Enrique R.; Yang, Ping

doi:10.1021/acs.jctc.7b00526

Cited by 21 publications

(19 citation statements)

References 75 publications

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“…While tailoring the HF exchange fraction , has been demonstrated to work well when optimizing for a single class of materials and properties, e.g., spin-splitting energies of Fe(II)/N spin-crossover complexes, this approach can fail across broader ranges of materials. , The optimal exchange fraction in a hybrid GGA or meta-GGA is strongly metal- or ligand-dependent in spin-state ordering (Figure ). ,,,,− Differences in exchange sensitivity for ligand dissociation energies or steps in a catalytic cycle create additional complications for typically studied properties of transition-metal complexes. , One type of physically motivated tuning (i.e., like DFT+U) is the use of optimally tuned range-separated hybrids, − wherein the range-separation parameter for incorporating HF exchange is used to eliminate deviations from piecewise linearity for each specific molecule with some improvement noted for transition-metal complex properties. ,− …”

Section: Molecular Modeling For Transition-metal Chemistrymentioning

confidence: 99%

Computational Discovery of Transition-metal Complexes: From High-throughput Screening to Machine Learning

et al. 2021

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Transition-metal complexes are attractive targets for the design of catalysts and functional materials. The behavior of the metal−organic bond, while very tunable for achieving target properties, is challenging to predict and necessitates searching a wide and complex space to identify needles in haystacks for target applications. This review will focus on the techniques that make high-throughput search of transition-metal chemical space feasible for the discovery of complexes with desirable properties. The review will cover the development, promise, and limitations of "traditional" computational chemistry (i.e., force field, semiempirical, and density functional theory methods) as it pertains to data generation for inorganic molecular discovery. The review will also discuss the opportunities and limitations in leveraging experimental data sources. We will focus on how advances in statistical modeling, artificial intelligence, multiobjective optimization, and automation accelerate discovery of lead compounds and design rules. The overall objective of this review is to showcase how bringing together advances from diverse areas of computational chemistry and computer science have enabled the rapid uncovering of structure−property relationships in transition-metal chemistry. We aim to highlight how unique considerations in motifs of metal−organic bonding (e.g., variable spin and oxidation state, and bonding strength/nature) set them and their discovery apart from more commonly considered organic molecules. We will also highlight how uncertainty and relative data scarcity in transition-metal chemistry motivate specific developments in machine learning representations, model training, and in computational chemistry. Finally, we will conclude with an outlook of areas of opportunity for the accelerated discovery of transition-metal complexes.

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Section: Molecular Modeling For Transition-metal Chemistrymentioning

confidence: 99%

Computational Discovery of Transition-metal Complexes: From High-throughput Screening to Machine Learning

et al. 2021

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“…A Perdew−Burke− Ernzerhof (PBE)-based hybrid functional with range-separated exchange and a three-parameter error-function range separation was set up for these calculations. The parameters were chosen as α = 0.25, β = 0.75, and γ = 0.15, as recommended previously for uranium complexes 89 to achieve a small DE without "tuning" the parameters for each complex individually. This tuned long-range corrected parametrization is labeled herein as TCL-PBE.…”

Section: Computational Detailsmentioning

confidence: 99%

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

Sergentu

Feng

et al. 2021

Inorg. Chem.

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A comprehensive ab initio study of periodic actinide−ligand bonding trends for trivalent actinides is performed. Relativistic density functional theory (DFT) and complete activespace (CAS) self-consistent field wavefunction calculations are used to dissect the chemical bonding in the [AnCl 6 ] 3− , [An-(CN) 6 ] 3− , [An(NCS) 6 ] 3− , [An(S 2 PMe 2 ) 3 ], [An(DPA) 3 ] 3− , and [An(HOPO)] − series of actinide (An = U−Es) complexes. Except for some differences for the early actinide complexes with DPA, bond orders and excess 5f-shell populations from donation bonding show qualitatively similar trends in 5f n active-space CAS vs DFT calculations. The influence of spin−orbit coupling on donation bonding is small for the tested systems. Along the actinide series, chemically soft vs chemically harder ligands exhibit clear differences in bonding trends. There are pronounced changes in the 5f populations when moving from Pu to Am or Cm, which correlate with previously noted "breaks" in chemical trends. Bonding involving 5f becomes very weak beyond Cm/Bk. We propose that Cm(III) is a borderline case among the trivalent actinides that can be meaningfully considered to be involved in ground-state 5f covalent bonding.

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“…A good example of these functionals is the Coulomb attenuating method, CAM‐B3LYP functional, [ 36 ] which was developed to minimize deviations in charge‐transfer excitation energies and used in this work to reproduce the absorption spectra of both carbonate compounds. It is important to note the recent study of Yang et al, [ 37 ] which is the closer DFT study to heavy actinides using this class of functionals. In this context, this work represents one of the first studies where the performance of CAM‐B3LYP functional is applied to heavy actinides.…”

Section: Computational Detailsmentioning

confidence: 99%

Theoretical examination of covalency in berkelium(IV) carbonate complexes

Albrecht‐Schönzart

Hobart

Páez‐Hernández

et al. 2020

Int J of Quantum Chemistry

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Experimental studies on the speciation of berkelium in carbonate media have shown that complexation of berkelium(III) by carbonate results in spontaneous oxidation to berkelium(IV) and that multiple species can be present in solution. We studied two proposed structures present in solution based on theoretical comparisons with spectroscopic data previously reported for Bk(IV) carbonate solutions. The multiconfigurational character of the ground and low‐lying excited states in both complexes is demonstrated to result from the strong spin‐orbit coupling. Although bonding in Bk(IV) carbonate and carbonate‐hydroxide complexes is dominated by strong Coulombic forces, the presence of non‐negligible covalent character is supported by ligand‐field theory, natural localized orbitals, topological studies of the electron density, and energy transition state natural orbitals for chemical valence. Bond orders based on natural localized molecular orbitals show that BkOH bonds possess enhanced orbital overlap, which is reflected in the bond strength. This is also observed in the decomposition of the orbital interaction energy into individual deformation density pairs.

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Assessment of Tuned Range Separated Exchange Functionals for Spectroscopies and Properties of Uranium Complexes

Cited by 21 publications

References 75 publications

Computational Discovery of Transition-metal Complexes: From High-throughput Screening to Machine Learning

Computational Discovery of Transition-metal Complexes: From High-throughput Screening to Machine Learning

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

Theoretical examination of covalency in berkelium(IV) carbonate complexes

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