Gauging the Performance of Density Functionals for Lanthanide-Containing Molecules

Grimmel, Stephanie A.; Schoendorff, George; Wilson, Angela K.

doi:10.1021/acs.jctc.5b01193

Cited by 45 publications

(62 citation statements)

References 62 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A detailed assessment of approximate density functionals is crucial for drawing meaningful conclusions from quantum chemical studies of transitionmetal complexes and their reactions. [1][2][3][4][5][6][7][8][9][10][11] One of the few benchmark sets for large transition-metal complexes containing experimental gas-phase reference data is our WCCR10 reference set of ligand bonding energies. 12 The WCCR10 set comprises ten experimentally measured gas-phase ligand dissociation energies obtained from threshold collision-induced decay (T-CID) experiments.…”

Section: Introductionmentioning

confidence: 99%

Calculation of Ligand Dissociation Energies in Large Transition-Metal Complexes

Husch

Freitag

Reiher

2018

J. Chem. Theory Comput.

View full text Add to dashboard Cite

The accurate calculation of ligand dissociation (or equivalently, ligand binding) energies is crucial for computational coordination chemistry. Despite its importance, obtaining accurate ab initio reference data is difficult, and density-functional methods of uncertain reliability are chosen for feasibility reasons. Here, we consider advanced coupled-cluster and multiconfigurational approaches to reinvestigate our WCCR10 set of 10 gas-phase ligand dissociation energies [ J. Chem. Theory Comput. 2014, 10, 3092]. We assess the potential multiconfigurational character of all molecules involved in these reactions with a multireference diagnostic [ Mol. Phys. 2017, 115, 2110] in order to determine where single-reference coupled-cluster approaches can be applied. For some reactions of the WCCR10 set, large deviations of density-functional results including semiclassical dispersion corrections from experimental reference data had been observed. This puzzling observation deserves special attention here, and we tackle the issue (i) by comparing to ab initio data that comprise dispersion effects on a rigorous first-principles footing and (ii) by a comparison of density-functional approaches that model dispersion interactions in various ways. For two reactions, species exhibiting nonnegligible static electron correlation were identified. These two reactions represent hard problems for electronic structure methods and also for multireference perturbation theories. However, most of the ligand dissociation reactions in WCCR10 do not exhibit static electron correlation effects, and hence, we may choose standard single-reference coupled-cluster approaches to compare with density-functional methods. For WCCR10, the Minnesota M06-L functional yielded the smallest mean absolute deviation of 13.2 kJ mol out of all density functionals considered (PBE, BP86, BLYP, TPSS, M06-L, PBE0, B3LYP, TPSSh, and M06-2X) without additional dispersion corrections in comparison to the coupled-cluster results, and the PBE0-D3 functional produced the overall smallest mean absolute deviation of 4.3 kJ mol. The agreement of density-functional results with coupled-cluster data increases significantly upon inclusion of any type of dispersion correction. It is important to emphasize that different density-functional schemes available for this purpose perform equally well. The coupled-cluster dissociation energies, however, deviate from experimental results on average by 30.3 kJ mol. Possible reasons for these deviations are discussed.

show abstract

Section: Introductionmentioning

confidence: 99%

Calculation of Ligand Dissociation Energies in Large Transition-Metal Complexes

Husch

Freitag

Reiher

2018

J. Chem. Theory Comput.

View full text Add to dashboard Cite

show abstract

“…At higher HF‐exchange percentage, that is, donation in the 5d orbitals, the spin‐contamination is low, inducing a better energetic evaluation. However, this behavior is not general and, in cases where ligands are not involved in high charge transfer (for example trihalide lanthanide complexes), the energies are better evaluated by using lower HF exchange, with donation in the 4f orbitals.…”

Section: Resultsmentioning

confidence: 99%

“…reported an energy comparison between two density functionals, B3PW91 and B3LYP, and the MP2 method, using small core relativistic effective core potentials (RECP), and they chose B3PW91 for further chemical studies . Recently, the performance of several density functionals over energies of diatomic lanthanide molecules was evaluated by Grimmel et al . They showed that TPSS was one of the best density functionals, and that less accurate results were obtained when more Hartree–Fock exchange was included in the functional.…”

Section: Introductionmentioning

confidence: 99%

Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes

2017

View full text Add to dashboard Cite

The equilibrium between the radical phenanthroline complex Cp*2Sm(phen) and the coupling product (Cp*2Sm(phen))2 has been investigated based on quantum chemistry calculations. Topological analyses pointed out that the C−C bond created has a partial covalent character, explaining why both the monomeric and the dimeric forms exist in equilibrium. A large variety of density functionals have been tested to reproduce experimental thermodynamic data for this equilibrium. Finally, the PBE0‐D3 and M06‐2X functionals lead to a good evaluation of the energies and enable a correct description of the ligand to metal charge transfer, both in the 4f and 5d metal orbitals.

show abstract

“…Grimmel et al benchmarked a number of DFT functionals that range from LDA to double hybrid ones for predicting properties of Ln-containing molecules. 329 54 experimental HOFs of Ln species were employed as the reference data set. They proposed that 5.0 kcal/mol represented the “lanthanide chemical accuracy” based on the uncertainty of the experimental values.…”

Section: Modeling Transition Metal-containing Species Using Quantum Mmentioning

confidence: 99%

Metal Ion Modeling Using Classical Mechanics

2017

View full text Add to dashboard Cite

Metal ions play significant roles in numerous fields including chemistry, geochemistry, biochemistry, and materials science. With computational tools increasingly becoming important in chemical research, methods have emerged to effectively face the challenge of modeling metal ions in the gas, aqueous, and solid phases. Herein, we review both quantum and classical modeling strategies for metal ion-containing systems that have been developed over the past few decades. This Review focuses on classical metal ion modeling based on unpolarized models (including the nonbonded, bonded, cationic dummy atom, and combined models), polarizable models (e.g., the fluctuating charge, Drude oscillator, and the induced dipole models), the angular overlap model, and valence bond-based models. Quantum mechanical studies of metal ion-containing systems at the semiempirical, ab initio, and density functional levels of theory are reviewed as well with a particular focus on how these methods inform classical modeling efforts. Finally, conclusions and future prospects and directions are offered that will further enhance the classical modeling of metal ion-containing systems.

show abstract

Gauging the Performance of Density Functionals for Lanthanide-Containing Molecules

Cited by 45 publications

References 62 publications

Calculation of Ligand Dissociation Energies in Large Transition-Metal Complexes

Calculation of Ligand Dissociation Energies in Large Transition-Metal Complexes

Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes

Metal Ion Modeling Using Classical Mechanics

Contact Info

Product

Resources

About