Assessment of DFT Methods for Transition Metals with the TMC151 Compilation of Data Sets and Comparison with Accuracies for Main-Group Chemistry

Chan, Bun; Gill, Peter M. W.; Kimura, Masanari

doi:10.1021/acs.jctc.9b00239

Cited by 122 publications

(156 citation statements)

References 68 publications

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“…Further performance assessment of the presently proposed cWFT methods is especially desirable for transition metal (and heavy p-block) energetics and barrier heights, particularly in order to learn their limitations. Toward that aim, we shall consider the following data sets in future work: TMC151 of transition metals; 112 CUAGAU of small copper, silver, and gold compounds; 113 the MOBH35 (metal–organic barrier height) data set; 110 , 111 and for the main group, the heavy p-block subset from ref ( 53 ) and the smaller MG8 of noncovalent interactions, isomerization reactions, thermochemistry, and barrier heights. 114 …”

Section: Resultsmentioning

confidence: 99%

Canonical and DLPNO-Based G4(MP2)XK-Inspired Composite Wave Function Methods Parametrized against Large and Chemically Diverse Training Sets: Are They More Accurate and/or Robust than Double-Hybrid DFT?

Semidalas

Martin

2020

J. Chem. Theory Comput.

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The large and chemically diverse GMTKN55 benchmark was used as a training set for parametrizing composite wave function thermochemistry protocols akin to G4(MP2)XK theory Karton, A.; Raghavachari, K. J. Chem. Theory Comput. 2019, 15, 4478−4484). On account of their availability for elements H through Rn, Karlsruhe def2 basis sets were employed. Even after reparametrization, the GMTKN55 WTMAD2 (weighted mean absolute deviation, type 2) for G4(MP2)-XK is actually inferior to that of the best rung-4 DFT functional, ωB97M-V. By increasing the basis set for the MP2 part to def2-QZVPPD, we were able to substantially improve performance at modest cost (if an RI-MP2 approximation is made), with WTMAD2 for this G4(MP2)-XK-D method now comparable to the better rung-5 functionals (albeit at greater cost). A three-tier approach with a scaled MP3/def2-TZVPP intermediate step, however, leads to a G4(MP3)-D method that is markedly superior to even the best double hybrids ωB97M(2) and revDSD-PBEP86-D4. Evaluating the CCSD(T) component with a triple-ζ, rather than split-valence, basis set yields only a modest further improvement that is incommensurate with the drastic increase in computational cost. G4(MP3)-D and G4(MP2)-XK-D have about 40% better WTMAD2, at similar or lower computational cost, than their counterparts G4 and G4(MP2), respectively: detailed comparison reveals that the difference lies in larger molecules due to basis set incompleteness error. An E2/ {T,Q} extrapolation and a CCSD(T)/def2-TZVP step provided the G4-T method of high accuracy and with just three fitted parameters. Using KS orbitals in MP2 leads to the G4(MP3|KS)-D method, which entirely eliminates the CCSD(T) step and has no steps costlier than scaled MP3; this shows a path forward to further improvements in double-hybrid density functional methods. None of our final selections require an empirical HLC correction; this cuts the number of empirical parameters in half and avoids discontinuities on potential energy surfaces. G4-T-DLPNO, a variant in which post-MP2 corrections are evaluated at the DLPNO-CCSD(T) level, achieves nearly the accuracy of G4-T but is applicable to much larger systems.

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Section: Resultsmentioning

confidence: 99%

Canonical and DLPNO-Based G4(MP2)XK-Inspired Composite Wave Function Methods Parametrized against Large and Chemically Diverse Training Sets: Are They More Accurate and/or Robust than Double-Hybrid DFT?

Semidalas

Martin

2020

J. Chem. Theory Comput.

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“…30 The accuracy of CC methods, most frequently CCSD(T), is often assumed to carry over to transition metal systems, as evidenced by a number of studies that have attempted to draw conclusions about the accuracy of DFT by comparing against reference CC values. [31][32][33][34][35] However, the reliability of CC methods for transition metal systems, even when multireference effects are approximated, has been the subject of vigorous debate, as illustrated by recent studies on transition metal diatomic-ligand systems. 24,[36][37][38][39][40][41] de Oliveira-Filho and co-workers found that even multireference CCSD(T) could not predict the bond dissociation energies (BDEs) for some diatomics accurately with respect to experimental measurements.…”

Section: Introductionmentioning

confidence: 99%

Predicting Ligand-Dissociation Energies of 3d Coordination Complexes with Auxiliary-Field Quantum Monte Carlo

Rudshteyn

Coskun

Weber

et al. 2020

J. Chem. Theory Comput.

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Transition metal complexes are ubiquitous in biology and chemical catalysis, yet they remain difficult to accurately describe with ab initio methods due to the presence of a large degree of dynamic electron correlation, and, in some cases, strong static correlation which results from a manifold of low-lying states. Progress has been hindered by a scarcity of high quality gas-phase experimental data, while exact ab initio predictions are usually computationally unaffordable due to the large size of the relevant complexes.In this work, we present a data set of 34 tetrahedral, square planar, and octahedral 3d metal-containing complexes with gas-phase ligand-dissociation energies that have reported uncertainties of ≤ 2 kcal/mol. We perform all-electron phaseless auxiliaryfield quantum Monte Carlo (ph-AFQMC) calculations utilizing multi-determinant trial wavefunctions selected by a blackbox procedure. We compare the results with those from density functional theory (DFT) with the B3LYP, B97, M06, PBE0, ωB97X-V, and DSD-PBEP86/2013 functionals, and a localized orbital variant of coupled cluster theory with single, double, and perturbative triple excitations (DLPNO-CCSD(T)). We find mean averaged errors of 1.09 ± 0.28 kcal/mol for our best ph-AFQMC method, vs 2.89 kcal/mol for DLPNO-CCSD(T) and 1.57 -3.87 kcal/mol for DFT. We find maximum errors of 2.96 ± 1.71 kcal/mol for our best ph-AFQMC method, vs 9.15 kcal/mol for DLPNO-CCSD(T) and 5.98 -13.69 kcal/mol for DFT. The reasonable performance of a number of DFT functionals is in stark contrast to the much poorer accuracy previously demonstrated for diatomic species, suggesting a moderation in electron correlation due to ligand coordination. However, the unpredictably large errors for a small subset of cases with both DFT and DLPNO-CCSD(T) methods leave cause for concern, especially in light of the unreliability of common multi-reference indicators. In contrast, the robust and, in principle, systematically improvable results of ph-AFQMC for these realistic complexes establish the method as a useful tool for elucidating the electronic structure of transition metal-containing complexes and predicting their gas-phase properties.

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“…[9,29] An octahedral ligand field splits the d manifold of the metal into t 2g and e g orbitals. While the results presented here were obtained with single reference Density Functional Theory (DFT), [33,34] the ωB97M-V functional [31] has proved very accurate both for main group [35,36] and transition metal [37] chemical energy differences. Spin crossover occurs in transition metal complexes when the energy required to pair spins to reach a low spin configuration is offset by the cost of maintaining a high spin configuration due to an increase in~O.…”

Section: Co] 2 +mentioning

confidence: 93%

“…[30] With a guiding hypothesis that uniform mechanical stress that compresses the molecule forces electron pairing and hence favors low spin states, we proceeded to apply hydrostatic pressure to first row transition metals with a homogeneous octahedral ligand field consisting of molecular hydrogen, nitrogen, and carbon monoxide, using the ωB97M-V [31] /def2-TZVP [32] level of theory. While the results presented here were obtained with single reference Density Functional Theory (DFT), [33,34] the ωB97M-V functional [31] has proved very accurate both for main group [35,36] and transition metal [37] chemical energy differences.…”

Section: Quantum Chemical Modeling Of Pressure-induced Spin Crossovermentioning

confidence: 99%

Quantum Chemical Modeling of Pressure‐Induced Spin Crossover in Octahedral Metal‐Ligand Complexes

2019

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Spin state switching on external stimuli is a phenomenon with wide applicability, ranging from molecular electronics to gas activation in nanoporous frameworks. Here, we model the spin crossover as a function of the hydrostatic pressure in octahedrally coordinated transition metal centers by applying a field of effective nuclear forces that compress the molecule towards its centroid. For spin crossover in first-row transition metals coordinated by hydrogen, nitrogen, and carbon monoxide, we find the pressure required for spin transition to be a function of the ligand position in the spectrochemical sequence. While pressures on the order of 1 GPa are required to flip spins in homogeneously ligated octahedral sites, we demonstrate a fivefold decrease in spin transition pressure for the archetypal strong field ligand carbon monoxide in octahedrally coordinated Fe 2 + in [Fe(II)(NH 3 ) 5 CO] 2 + .Pressure-induced spin-flips of transition metal sites involve changes in Coulomb energy, closed shell repulsions, covalent bonding energy and crystal field energy. [1,2] Using the computational Extreme-Pressure PCM (XP-PCM) protocol, [3][4][5] it has been shown that high pressures cause drastic electronic rearrangements, causing first row transition metals with electronic configurations d n (4 � n � 8) to favor low spin configurations at high pressures. [6] In a metal-organic framework (MOF) with exposed Fe(II) sites, a distinct step as a function of atmospheric pressure has been observed in the adsorption isotherm of carbon monoxide, for which a cooperative spin-transition mechanism involving interacting iron centers in the MOF on introduction of the strong-field ligand carbon monoxide has been proposed. [7] In general, the use of MOFs in the separation of industrially relevant gases like hydrogen, nitrogen and carbon monoxide holds a lot of promise, due to the large surface areas, the thermal stability and the adjustability of various parameters of the MOFs. [8] The smallest building block of spin crossover systems is often an octahedrally coordinated transition metal center with its 3d orbitals split by the ligand field environment. Spin-flip at high pressures can be attributed to the increase in splitting of the 3d levels at the metal site such that the potential energy required to maintain a high spin configuration surpasses the spin pairing energy. [9] Using effective nuclear forces scaled by their distances from the molecular centroid we here model spin crossover in octahedral metal-ligand complexes as a function of hydrostatic pressure. We find the pressure required for spin transition to be a function of ligand position in the spectrochemical sequence [10] and demonstrate that the spin transition pressure can be tuned by an adequate choice of the ligand field. Finer quantum chemical effects at play in the process involve a change in the covalent binding energy, Pauli repulsion, and charge transfer as a function of pressure, as demonstrated with an Energy Decomposition Analysis (EDA) [11] scheme.Any external force on...

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Assessment of DFT Methods for Transition Metals with the TMC151 Compilation of Data Sets and Comparison with Accuracies for Main-Group Chemistry

Cited by 122 publications

References 68 publications

Canonical and DLPNO-Based G4(MP2)XK-Inspired Composite Wave Function Methods Parametrized against Large and Chemically Diverse Training Sets: Are They More Accurate and/or Robust than Double-Hybrid DFT?

Canonical and DLPNO-Based G4(MP2)XK-Inspired Composite Wave Function Methods Parametrized against Large and Chemically Diverse Training Sets: Are They More Accurate and/or Robust than Double-Hybrid DFT?

Predicting Ligand-Dissociation Energies of 3d Coordination Complexes with Auxiliary-Field Quantum Monte Carlo

Quantum Chemical Modeling of Pressure‐Induced Spin Crossover in Octahedral Metal‐Ligand Complexes

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