Benchmarks of the density functional tight-binding method for redox, protonation and electronic properties of quinones

Kitheka, Maureen; Redington, Morgan C.; Zhang, Jibo; Yao, Yan; Goyal, Puja

doi:10.1039/d1cp05333g

Cited by 3 publications

(4 citation statements)

References 117 publications

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“…As reported earlier by us and others, DFTB3-D3 underestimates the lattice parameters, but re-optimization of the DFTB3-D3-predicted structures with DFT-D3 leads to lattice parameters closer to the experimental values. 17 The calculated lattice energies using PBE-D3 were found to have a mean absolute error of only 4.3 kJ/mol or ~1 kcal/mol, the maximum error being only 6.4 kJ/mol or ~1.5 kcal/mol. The trends observed in the calculated lattice energies for different molecules are similar to those observed by Reilly and Tkatchenko 23 using the Tkatchenko-Scheffler (TS) 34 and many-body dispersion (MBD) corrections with the PBE and hybrid PBE functionals.…”

Section: Discussionmentioning

confidence: 93%

“…Its computational expense is, however, not negligible. As highlighted in our previous study, 17 a computationally efficient yet accurate method for modeling organic electrode materials in batteries is highly desirable. Being two-three orders of magnitude faster than DFT, the density functional tight-binding (DFTB) 18 method is a very promising option in this regard.…”

Section: Introductionmentioning

confidence: 99%

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Organic Molecular Crystal Structure Prediction Using the Density Functional Tight Binding (Dftb) Method

Kitheka

Jing

Yao

et al. 2023

Preprint

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Over the years, crystal structure prediction (CSP) has thrived as an area of research, spanning various scientific disciplines and having significant applications in industries such as pharmaceuticals and agrochemicals. Within the field of batteries, redox-active organic materials (ROMs) such as quinones have received increased attention as promising electrode materials for rechargeable batteries. However, experimental determination of the crystal structure of intermediate species formed during the discharge/charge cycle can often be challenging. Incomplete X-ray diffraction patterns can also lead to difficulties in crystal structure determination for ROMs used in batteries. Here, we systematically investigate the ability of the third-order density functional tight binding method (DFTB3) in conjunction with the particle swarm optimization (PSO) algorithm, as implemented in the CALYPSO software, to predict the crystal structures of different classes of organic molecules chosen from the X23 data set. We also apply this approach to predict the crystal structures of selected quinones. Our findings emphasize the potential of CALYPSO/DFTB as a promising approach for CSP of different classes of organic molecules, including quinones. Additionally, they establish the foundation for future CSP studies of other organic molecules utilized in rechargeable batteries.

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Section: Discussionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Organic Molecular Crystal Structure Prediction Using the Density Functional Tight Binding (Dftb) Method

Kitheka

Jing

Yao

et al. 2023

Preprint

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show abstract

Section: Discussionmentioning

confidence: 93%

Efficient Organic Molecular Crystal Structure Prediction Using the Density Functional Tight-Binding Method

Kitheka,

Jing,

Yao

et al. 2023

Preprint

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Over the years, crystal structure prediction (CSP) has thrived as an area of research, spanning various scientific disciplines, and having significant applications in industries such as pharmaceuticals and agrochemicals. Within the field of batteries, redox-active organic materials (ROMs) such as quinones have received increased attention as promising electrode materials for rechargeable batteries. However, experimental determination of the crystal structure of intermediate species formed during the discharge/charge cycle can often be challenging. Incomplete X-ray diffraction patterns can also lead to difficulties in crystal structure determination for ROMs used in batteries. Use of a semiempirical electronic structure method for CSP helps to avoid force field reparameterization for different species, sometimes with complex electronic structure, formed during battery operation. It also helps to significantly lower the computational cost compared to the widely used density functional theory (DFT). The goal of this study is to systematically investigate the ability of a DFT-based semiempirical method, third-order density functional tight-binding (DFTB3), to predict the most stable crystal structures of organic molecules with different kinds of intermolecular interactions ranging from hydrogen bonding to -stacking. Here, DFTB3 in conjunction with the particle swarm optimization (PSO) algorithm, as implemented in the CALYPSO software, is also used to predict the most stable crystal structures of selected quinones relevant to organic batteries. Our findings emphasize the potential of CALYPSO/DFTB as a promising approach for CSP of different classes of organic molecules, including quinones. Additionally, they establish the foundation for future CSP studies of other organic molecules utilized in rechargeable batteries.

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“…Unrestricted B3LYP was used for the open-shell one-electron reduced radicals. This combination of method and basis set is a popular choice that has been tested extensively for quinones in combination with implicit solvation. ,, A mixed basis set was used for iodine-containing molecules, treating iodine with the def2TZVP basis set with an effective core potential and remaining atoms with 6-311++G(d,p). Frequency calculations were used to check for imaginary frequencies.…”

Section: Methodsmentioning

confidence: 99%

First and Second Reductions in an Aprotic Solvent: Comparing Computational and Experimental One-Electron Reduction Potentials for 345 Quinones

Elhajj,

Gozem

2024

J. Chem. Theory Comput.

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Using reference reduction potentials of quinones recently measured relative to the saturated calomel electrode (SCE) in N,Ndimethylformamide (DMF), we benchmark absolute one-electron reduction potentials computed for 345 Q/Q •− and 265 Q •− /Q 2− half-reactions using adiabatic electron affinities computed with density functional theory and solvation energies computed with four continuum solvation models: IEF-PCM, C-PCM, COSMO, and SM12. Regression analyses indicate a strong linear correlation between experimental and absolute computed Q/Q •− reduction potentials with Pearson's correlation coefficient (r) between 0.95 and 0.96 and the mean absolute error (MAE) relative to the linear fit between 83.29 and 89.51 mV for different solvation methods when the slope of the regression is constrained to 1. The same analysis for Q •− /Q 2− gave a linear regression with r between 0.74 and 0.90 and MAE between 95.87 and 144.53 mV, respectively. The y-intercept values obtained from the linear regressions are in good agreement with the range of absolute reduction potentials reported in the literature for the SCE but reveal several sources of systematic error. The y-intercepts from Q •− / Q 2− calculations are lower than those from Q/Q •− by around 320−410 mV for IEF-PCM, C-PCM, and SM12 compared to 210 mV for COSMO. Systematic errors also arise between molecules having different ring sizes (benzoquinones, naphthoquinones, and anthraquinones) and different substituents (titratable vs nontitratable). SCF convergence issues were found to be a source of random error that was slightly reduced by directly optimizing the solute structure in the continuum solvent reaction field. While SM12 MAEs were lower than those of the other solvation models for Q/Q •− , SM12 had larger MAEs for Q •− /Q 2− pointing to a larger error when describing multiply charged anions in DMF. Altogether, the results highlight the advantages of, and further need for, testing computational methods using a large experimental data set that is not skewed (e.g., having more titratable than nontitratable substituents on different parent groups or vice versa) to help further distinguish between sources of random and systematic errors in the calculations.

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Benchmarks of the density functional tight-binding method for redox, protonation and electronic properties of quinones

Abstract: Organic materials with controllable molecular design and sustainable resources are promising electrode materials. Crystalline quinones have been investigated in a variety of rechargeable battery chemistries due to their ubiquitous nature,...

Cited by 3 publications

References 117 publications

Organic Molecular Crystal Structure Prediction Using the Density Functional Tight Binding (Dftb) Method

Organic Molecular Crystal Structure Prediction Using the Density Functional Tight Binding (Dftb) Method

Efficient Organic Molecular Crystal Structure Prediction Using the Density Functional Tight-Binding Method

First and Second Reductions in an Aprotic Solvent: Comparing Computational and Experimental One-Electron Reduction Potentials for 345 Quinones

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