Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated?

Brorsen, Kurt R.; Yang, Yang; Pak, Michael V.; Hammes‐Schiffer, Sharon

doi:10.1021/acs.jpclett.7b00774

Cited by 74 publications

(81 citation statements)

References 37 publications

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“…As shown by the data in Table 1, B2PLYP on average is nearly as good as MP2 for the same atomic set considered (26). A recent analysis on the correlation of bond energies and bond densities for diatomic molecules also suggested the good behavior of the B2PLYP functional (36).…”

Section: Resultsmentioning

confidence: 65%

Doubly hybrid density functionals that correctly describe both density and energy for atoms

Zhu

2018

Proc. Natl. Acad. Sci. U.S.A.

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Recently, it was argued [Medvedev MG, et al. (2017) 355:49-52] that the development of density functional approximations (DFAs) is "straying from the path toward the exact functional." The exact functional should yield both exact energy and density for a system of interest; nevertheless, they found that many heavily fitted functionals for molecular energies actually lead to poor electron densities of atoms. They also observed a trend that, for the nonempirical and few-parameter functionals, densities can be improved as one climbs up the first four rungs of the Jacob's ladder of DFAs. The XYG3 type of doubly hybrid functionals (xDHs) represents a less-empirical and fewer-parameter functional on the top fifth rung, in which both the Hartree-Fock-like exchange and the second-order perturbative (MP2-like) correlation are hybridized with the low rung functionals. Here, we show that xDHs can well describe both density and energy for the same atomic set of Medvedev et al., showing that the latter trend can well be extended to the top fifth rung.

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Section: Resultsmentioning

confidence: 65%

Doubly hybrid density functionals that correctly describe both density and energy for atoms

Zhu

2018

Proc. Natl. Acad. Sci. U.S.A.

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“…Recent studies suggest that some of the modern functionals deviate from the theory and principles of DFT. 67,68 This results in the correct answer being obtained for the wrong reason or based on ill-defined physical properties. This viewpoint has been later debated in a series of follow-up papers, keeping the discussion on the accuracy of DFT methods open.…”

Section: Competition Between Methods and Model Accuracies In Computatimentioning

confidence: 99%

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

et al. 2018

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Computational chemistry provides a versatile toolbox for studying mechanistic details of catalytic reactions and holds promise to deliver practical strategies to enable the rational in silico catalyst design. The versatile reactivity and nontrivial electronic structure effects, common for systems based on 3d transition metals, introduce additional complexity that may represent a particular challenge to the standard computational strategies. In this review, we discuss the challenges and capabilities of modern electronic structure methods for studying the reaction mechanisms promoted by 3d transition metal molecular catalysts. Particular focus will be placed on the ways of addressing the multiconfigurational problem in electronic structure calculations and the role of expert bias in the practical utilization of the available methods. The development of density functionals designed to address transition metals is also discussed. Special emphasis is placed on the methods that account for solvation effects and the multicomponent nature of practical catalytic systems. This is followed by an overview of recent computational studies addressing the mechanistic complexity of catalytic processes by molecular catalysts based on 3d metals. Cases that involve noninnocent ligands, multicomponent reaction systems, metal–ligand and metal–metal cooperativity, as well as modeling complex catalytic systems such as metal–organic frameworks are presented. Conventionally, computational studies on catalytic mechanisms are heavily dependent on the chemical intuition and expert input of the researcher. Recent developments in advanced automated methods for reaction path analysis hold promise for eliminating such human-bias from computational catalysis studies. A brief overview of these approaches is presented in the final section of the review. The paper is closed with general concluding remarks.

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“…Interestingly, arriving at an analogous long-range HF exchange, [222][223][224] TT-ωPBEh shows a comparable predictive power to OT-ωPBEh and PBE0, and a smaller AE than B3LYP for three quarters of To extend our discussion, we also explored the sensitivity of TT-ωPBEh on T 1 to the charge separation extent in the space. [9][10][11][12][13][14][15][16]225 Due to the SIE and the inaccurate adiabatic local density approximation (ALDA) in TDDFT, poor performance is expected for a severe charge transfer T 1 state using TT-ωPBEh. To visualize our argument, we illustrate HONTO and LUNTO for the T 1 states of two TADF emitters, 4CzTPN and PhCz, in the right panel of Fig.…”

Section: Charge Transfer Triplet Statementioning

confidence: 99%

Triplet Tuning: A Novel Family of Non-Empirical Exchange–Correlation Functionals

Lin

Voorhis

2019

J. Chem. Theory Comput.

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In the framework of density functional theory (DFT), the lowest triplet excited state, T 1 , can be evaluated using multiple formulations, the most straightforward of which are unrestricted DFT (UDFT) and time-dependent DFT (TDDFT). Assuming the exact exchangecorrelation (XC) functional is applied, UDFT and TDDFT provide identical energies for T 1 (E T ), which is also a constraint that we require our XC functionals to obey. However, this condition is not satisfied by most of the popular XC functionals, leading to inaccurate predictions of low-lying, spectroscopically and photochemically important excited states, such as T 1 and the lowest singlet excited state (S 1 ). Inspired by the optimal tuning strategy for frontier orbital energies [T. Stein, L. Kronik, and R. Baer, J. Am. Chem. Soc. 131, 2818 (2009)], we proposed a novel and non-empirical prescription of constructing an XC functional in which the agreement between UDFT and TDDFT in E T is strictly enforced. Referred to as "triplet tuning", our procedure allows us to formulate the XC functional on a case-by-case basis using the molecular structure as the exclusive input, without fitting to any experimental data. The first triplet tuned XC functional, TT-ωPBEh, is formulated as a long-range-corrected (LRC) hybrid of Perdew-Burke-Ernzerhof (PBE) and Hartree-Fock (HF) functionals [M. A. Rohrdanz, K. M. Martins, and J. M. Herbert, J. Chem. Phys. 130, 054112 (2009)] and tested on four sets of large organic molecules. Compared to existing functionals, TT-ωPBEh manages to provide 1 arXiv:1806.00317v3 [physics.chem-ph] 15 Jan 2019more accurate predictions for key spectroscopic and photochemical observables, including but not limited to E T , the optical band gap (E S ), the singlet-triplet gap (∆E ST ), and the vertical ionization potential (I ⊥ ), as it adjusts the effective electron-hole interactions to arrive at the correct excitation energies. This promising triplet tuning scheme can be applied to a broad range of systems that were notorious in DFT for being extremely challenging.

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Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated?

Cited by 74 publications

References 37 publications

Doubly hybrid density functionals that correctly describe both density and energy for atoms

Doubly hybrid density functionals that correctly describe both density and energy for atoms

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

Triplet Tuning: A Novel Family of Non-Empirical Exchange–Correlation Functionals

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