Evaluating the harmonic approximation for the prediction of thermodynamic formation properties of solids

Fromsejer, Rasmus; Maribo-Mogensen, Bjørn; Kontogeorgis, Georgios M.

doi:10.1016/j.commatsci.2023.112152

Cited by 4 publications

(2 citation statements)

References 92 publications

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“…In these cases, Density Functional Theory (DFT) [9,10] may provide an alternative source of information. Since DFT can give both the ground state electronic energy as well as the vibrational spectrum [11][12][13], it can be combined with statistical thermodynamics to yield all relevant and necessary thermodynamic quantities [14,15]. A quantity such as the equilibrium composition, which is of paramount importance in process design, is, however, rather complex; it combines many ingredients.…”

Section: Introductionmentioning

confidence: 99%

“…In the last 10-20 years, the number of studies that have benchmarked a specific property calculated from DFT or used a more advanced computational method has been increasing [13,[16][17][18][19][20][21][22][23][24][25][26][27][28][29]. However, very few of them have focused on the complex issue of predicting the equilibrium composition systematically.…”

Section: Introductionmentioning

confidence: 99%

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Benchmarking First-Principles Reaction Equilibrium Composition Prediction

et al. 2023

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The availability of thermochemical properties allows for the prediction of the equilibrium compositions of chemical reactions. The accurate prediction of these can be crucial for the design of new chemical synthesis routes. However, for new processes, these data are generally not completely available. A solution is the use of thermochemistry calculated from first-principles methods such as Density Functional Theory (DFT). Before this can be used reliably, it needs to be systematically benchmarked. Although various studies have examined the accuracy of DFT from an energetic point of view, few studies have considered its accuracy in predicting the temperature-dependent equilibrium composition. In this work, we collected 117 molecules for which experimental thermochemical data were available. From these, we constructed 2648 reactions. These experimentally constructed reactions were then benchmarked against DFT for 6 exchange–correlation functionals and 3 quality of basis sets. We show that, in reactions that do not show temperature dependence in the equilibrium composition below 1000 K, over 90% are predicted correctly. Temperature-dependent equilibrium compositions typically demonstrate correct qualitative behavior. Lastly, we show that the errors are equally caused by errors in the vibrational spectrum and the DFT electronic ground state energy.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Benchmarking First-Principles Reaction Equilibrium Composition Prediction

et al. 2023

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Accurate formation enthalpies of solids using reaction networks

Fromsejer,

Maribo-Mogensen,

Kontogeorgis

et al. 2024

npj Comput Mater

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Crystalline solids play a fundamental role in a host of materials and technologies, ranging from pharmaceuticals to renewable energy. The thermodynamic properties of these solids are crucial determinants of their stability and therefore their behavior. The advent of large density functional theory databases with properties of solids has stimulated research on predictive methods for their thermodynamic properties, especially for the enthalpy of formation ΔfH. Increasingly sophisticated artificial intelligence and machine learning (ML) models have primarily driven development in this field in recent years. However, these models can suffer from lack of generalizability and poor interpretability. In this work, we explore a different route and develop and evaluate a framework for the application of reaction network (RN) theory to the prediction of ΔfH of crystalline solids. For an experimental dataset of 1550 compounds we are able to obtain a mean absolute error w.r.t ΔfH of 29.6 meV atom−1 using the RN approach. This performance is better than existing ML-based predictive methods and close to the experimental uncertainty. Moreover, we show that the RN framework allows for straightforward estimation of the uncertainty of the predictions.

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Lattice dynamics and elastic waves scattering by surrogate atoms in quasi-one dimensional atomic assemblies

Cheknoun,

Sait,

Bourahla

2024

Int. J. Mod. Phys. B

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An analytical and numerical formalism is developed to study the influence of the various positions of substitution atoms B on the scattering and transmission vibration modes in quasi-1D monatomic structures A. The matching technique is employed to calculate the dynamical properties and transmittance spectra of two substituted atomic sites. The theoretical formalism gives a complete description of the lattice dynamics and the vibration-waves propagation in the presence of the impurity sites. Numerical calculations are performed for three different positions of the two substituted atoms B in the low-dimensional structure consisting of double monatomic parallel chains. First, we examine the position where the two B atoms are adjacent in the y-direction, afterwards, we place the two sites side by side in the x-direction. Lastly, the two sites are placed in oblique configuration. The obtained results show that phonons associated to the inhomogeneous structures are strongly dependent on the scattering frequency, elastic force parameters and the position of the atomic substituted sites. In the three considered positions, the presence of the B atoms gives rise to localized vibration effects. The fluctuations observed in the vibration spectra are related to resonances due to the coherent coupling between travelling phonons and the localized vibration modes in the neighborhood of the impurity sites.

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Evaluating the harmonic approximation for the prediction of thermodynamic formation properties of solids

Cited by 4 publications

References 92 publications

Benchmarking First-Principles Reaction Equilibrium Composition Prediction

Benchmarking First-Principles Reaction Equilibrium Composition Prediction

Accurate formation enthalpies of solids using reaction networks

Lattice dynamics and elastic waves scattering by surrogate atoms in quasi-one dimensional atomic assemblies

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