Benchmarks and Reliable DFT Results for Spin Gaps of Small Ligand Fe(II) Complexes

Song, Suhwan; Kim, Min Cheol; Sim, Eunji; Benali, Anouar; Heinonen, Olle; Burke, Kieron

doi:10.1021/acs.jctc.7b01196

Cited by 89 publications

(159 citation statements)

References 77 publications

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“…These systemsa re not spin-crossover complexes, but they have been studied previously using several different methods, [27,31,[33][34][35][80][81][82] which serves as as ound basis for comparison of our OT-RSH results for spin-state energetics in general. These systemsa re not spin-crossover complexes, but they have been studied previously using several different methods, [27,31,[33][34][35][80][81][82] which serves as as ound basis for comparison of our OT-RSH results for spin-state energetics in general.…”

Section: Resultsmentioning

confidence: 99%

“…In principle, the diffusion Monte Carlo (DMC) andC ASPT2 methodsa re expected to be the most accurate. Very recently,S ong et al [82] reported ad ifferent set of DMC calculations (starting from B3LYP orbitals) also shown in Table 1. The DMC results of Droghetti et al, [27] given in the second row of Ta ble 1, suggest DE values that are high compared with those obtained from other methods.…”

Section: Resultsmentioning

confidence: 99%

“…Agreement of our OT-RSH results with the OPBE results [24] is mixed. Recently,S ong et al [82] studied complexes (1)-(3)w ith the density-corrected DFT (DC-DFT) method. However,i ft he unstablec losed-shell solution is used for the singlet,t he DE values agree better with values reported in the literature (see part 3o ft he Supporting Information for a more detailed discussion).…”

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Spin‐State Energetics of Fe Complexes from an Optimally Tuned Range‐Separated Hybrid Functional

Prokopiou

Kronik

2017

Chemistry A European J

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We assess the performance of the optimally tuned range-separated hybrid (OT-RSH) functional approach in predicting the ground-state electronic configuration and spin-state energetics of complexes that can potentially exhibit multiple spin configurations. To that end, we investigate eight iron complexes: four spin-crossover complexes, for which reference data from other approximate density functionals are available, and four smaller complexes, for which reference ab initio data are available. We show that the spin-state energetics are mostly governed by the percentage of short-range exact exchange and are only weakly influenced by the choice of the range-separation parameter. However, the electronic structure, especially the fundamental gap, is much more sensitive to the range-separation parameter. We further find that correct prediction of the ground state in spin-crossover compounds requires a reduction in the amount of short-range exact exchange, likely owing to a larger role of static correlation.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Spin‐State Energetics of Fe Complexes from an Optimally Tuned Range‐Separated Hybrid Functional

Prokopiou

Kronik

2017

Chemistry A European J

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“…19 and 20 dictate the following chain of inequalities: v ] are the density-driven terms, as they are given by the difference between the same energy functional evaluated on different densities. Generalizing the ideas of DC-DFT [13,14,21,22,23,24,25], for any pair of density functionals, we classify a ∆E v energy difference as energy-or density-driven. We consider energy-driven ∆E v as ones whose functional-driven terms in Eqs.…”

Section: Density Functional Analysismentioning

confidence: 99%

Density Functional Analysis: The Theory of Density-Corrected DFT

Vuckovic

Song

Kozlowski

et al. 2019

J. Chem. Theory Comput.

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136

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Density-corrected density functional theory (DC-DFT) is enjoying substantial success in improving semilocal DFT calculations in a wide variety of chemical problems. This paper provides the formal theoretical framework and assumptions for the analysis of any functional minimization with an approximate functional. We generalize DC-DFT to allow comparison of any two functionals, not just comparison with the exact functional. We introduce a linear interpolation between any two approximations, and use the results to analyze global hybrid density functionals. We define the basins of density-space in which this analysis should apply, and give quantitative criteria for when DC-DFT should apply. We also discuss the effects of strong correlation on density-driven error, utilizing the restricted HF Hubbard dimer as an illustrative example. arXiv:1908.05721v1 [physics.chem-ph]

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“…This demonstrates that an SDFT calculation can produce excellent total densities and energies, but poor spin densities. This well-known phenomenon has been observed, for example, in transition-metal complexes [7,[31][32][33].…”

Section: Magnetizationsmentioning

confidence: 68%

(Spin-)density-functional theory for open-shell systems: Exact magnetization density functional for the half-filled Hubbard trimer

Ullrich

2019

Phys. Rev. A

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According to the Hohenberg-Kohn theorem of density-functional theory (DFT), all observable quantities of systems of interacting electrons can be expressed as functionals of the ground-state density. This includes, in principle, the spin polarization (magnetization) of open-shell systems; the explicit form of the magnetization as a functional of the total density is, however, unknown. In practice, open-shell systems are always treated with spin-DFT, where the basic variables are the spin densities. Here, the relation between DFT and spin-DFT for open-shell systems is illustrated and the exact magnetization density functional is obtained for the half-filled Hubbard trimer. Errors arising from spin-restricted and -unrestricted exact-exchange Kohn-Sham calculations are analyzed and partially cured via the exact magnetization functional. I. INTRODUCTION: DFT VERSUS SDFTFor the z-components, only the diagonal matrix elements are nonzero, and we get immediatelyB z 7,7 = B z 12,12 = −B z2 B z 8,8 = B z 10,10 = −B z3 B z 9,9 = B z 11,11 = −B z1 B z 13,13 = B z 18,18 = B z2 B z 14,14 = B z 16,16 = B z3 B z 15,15 = B z 17,17 = B z1 B z 19,19 = −B z1 − B z2 − B z3

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Benchmarks and Reliable DFT Results for Spin Gaps of Small Ligand Fe(II) Complexes

Cited by 89 publications

References 77 publications

Spin‐State Energetics of Fe Complexes from an Optimally Tuned Range‐Separated Hybrid Functional

Spin‐State Energetics of Fe Complexes from an Optimally Tuned Range‐Separated Hybrid Functional

Density Functional Analysis: The Theory of Density-Corrected DFT

(Spin-)density-functional theory for open-shell systems: Exact magnetization density functional for the half-filled Hubbard trimer

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