First-principles calculations of solid-phase enthalpy of formation of energetic materials

Abstract The solid-phase enthalpy of formation (∆H f, solid ) of energetic materials was generally predicted from the gas-phase enthalpy of formation (∆H f, gas ) and sublimation enthalpy (∆H sub ). Here, the standard ∆H f, solid of energetic materials is directly obtained from density functional th...

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Bibliographic Details
Main Authors: Lixiang Zhong, Danyang Liu, Maoxin Hu, Xiaoning Yang, Ruibin Liu, Yugui Yao
Format: Article
Language:English
Published: Nature Portfolio 2025-05-01
Series:Communications Chemistry
Online Access:https://doi.org/10.1038/s42004-025-01544-9
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Summary:Abstract The solid-phase enthalpy of formation (∆H f, solid ) of energetic materials was generally predicted from the gas-phase enthalpy of formation (∆H f, gas ) and sublimation enthalpy (∆H sub ). Here, the standard ∆H f, solid of energetic materials is directly obtained from density functional theory (DFT) calculations by computing the enthalpy difference between the solid-phase energetic material and its constituent elements in their reference states. To reduce the errors in DFT calculations, a concept of isocoordinated reaction is introduced, i.e., the reference states are selected based on the coordination numbers of all atoms in the energetic material. This DFT method for ∆H f, solid calculation does not require experimental input, data fitting, or machine learning. For more than 150 energetic materials collected from the literature, the mean absolute error (MAE) of ∆H f, solid for the DFT method is 39 kJ mol−1 (or 9.3 kcal mol−1) referring to the literature. Our demonstration raises prospects for first-principles prediction of the properties of energetic materials, and the proposed method for ∆H f, solid calculation is also promising for other materials.
ISSN:2399-3669