Journal/Book/Conference Title Title
Advances in Physical Chemistry
Heat of formation is one of several important parameters used to assess the performance of energetic compounds. We evaluated the ability of six different methods to accurately calculate gas-phase heat of formation (Δ 𝑓𝐻𝑜 298,g) values for a test set of 45 nitrogencontaining energetic compounds. Density functional theory coupled with the use of isodesmic or other balanced equations yielded calculated results in which 82% (37 of 45) of the Δ 𝑓𝐻𝑜 298,g values were within ±2.0 kcal/mol of the most recently recommended experimental/reference values available. This was compared to a procedure using density functional theory (DFT) coupled with an atom and group contribution method in which 51% (23 of 45) of the Δ 𝑓𝐻𝑜 298,g values were within ±2.0 kcal/mol of these values. The T1 procedure and Benson’s group additivity method yielded results in which 51% (23 of 45) and 64% (23 of 36) of the Δ 𝑓𝐻𝑜 298,g values, respectively, were within ±2.0 kcal/mol of these values. We also compared two relatively new semiempirical approaches (PM7 and RM1) with regard to their ability to accurately calculate Δ 𝑓𝐻𝑜 298,g. Although semiempirical methods continue to improve, they were found to be less accurate than the other approaches for the test set used in this investigation.
Department of Chemistry and Biochemistry
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UNI ScholarWorks, University of Northern Iowa, Rod Library
©2016 Michael S. Elioff, Jordan Hoy, and John A. Bumpus. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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This work is licensed under a Creative Commons Attribution 4.0 License.
Elioff, Michael S.; Hoy, Jordon; and Bumpus, John A., "Calculating Heat of Formation Values of Energetic Compounds: A Comparative Study" (2016). Faculty Publications. 1.