Quantum Chemical Investigation of Perchloric Acid Decomposition Releasing Oxygen

Chatterjee, Tanusree; Thynell, Stefan T.

doi:10.1021/acs.jpca.1c04433

Cited by 2 publications

(2 citation statements)

References 35 publications

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“…DFT calculations can quickly obtain reliable information about the paths and energy barriers of chemical processes while obtaining accurate charge density data for atoms in a molecule. − Along this line, we expect to establish the correlation between their reaction barriers and the charge densities of N 1 and N 2 by DFT calculation, which can guide the synthesis of new tetrazole-fused energetic materials.…”

Section: Introductionmentioning

confidence: 99%

Exploring the Correlation between Azido-Tetrazolo Tautomerizations and Isomer Structures: Electron Density of Bonding N Atoms and N–N Bond Polarity

Wu,

Hu,

et al. 2024

J. Phys. Chem. A

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Azido-tetrazolo tautomerizations between azido N-heteroaromatic compounds and tetrazole-fused energetic materials can produce a new generation of high-energy density compounds. Density functional theory (DFT) computations are performed to explore the relationship between reaction barriers and electron densities of bonding N atoms, i.e., the terminal N 1 and heterocyclic N 2 atoms, for six reported tautomerizations. The results reveal four linear correlations between reverse reaction barriers (G r ) and the electron densities of N 1 and N 2 atoms in the product. N 1 electron density (ρ Nd 1 ) and N−N bond polarity, as measured by the difference between the electron densities on the two N atoms (Δρ N = ρ Nd 1 − ρ Nd 2 ) in products, are inversely proportional to the reverse reaction barriers. They are also proportional to the energy barrier differences between the forward and reverse reactions (ΔG = G f − G r ). Polar solvents, including DMSO, water, and acetone, can effectively increase the reverse reaction barriers (G r ) by improving the stability of products. This regularity is further confirmed by its application to four additional tautomerizations and can be used to screen out unfavorable azido-tetrazolo tautomerization reactions and increase the success rate of such synthesis.

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Section: Introductionmentioning

confidence: 99%

Exploring the Correlation between Azido-Tetrazolo Tautomerizations and Isomer Structures: Electron Density of Bonding N Atoms and N–N Bond Polarity

Wu,

Hu,

et al. 2024

J. Phys. Chem. A

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“…此外还有电子转移机理(图 2, Path-a). 对于 HClO 4 的分解, Chatterjee 等 [25] 提出了脱水机理(图 2, Path-d, Path-e). Zhu 等 [23][24]32,37] 对 AP 热分解过程中可能涉及的物种和反应途径进行了大量的理论计算.…”

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Density Functional Theory Study on Thermal Decomposition Mechanisms of Ammonium Perchlorate

Yang¹,

Ling²,

Li³

et al. 2023

Acta Chimica Sinica

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The thermal decomposition characteristics of ammonium perchlorate (AP) have a great influence on the performance of solid propellant. Although a large number of mechanistic studies have been published over the past few decades, there is no unified understanding of the decomposition yet, and the overall mechanism pathway is still unclear. In the present work, the thermal decomposition pathways of AP were studied systematically using broken-symmetry density functional theory method (BS-UB3LYP/6-311＋G (d,p). This method can describe the homo-cleavage process of covalent bond well, and locate the transition state with singlet-diradical characteristics. Compared with typical multireference method, brokensymmetry density functional theory (BS-UDFT) can give good results and is much faster, and therefore is highly convenient for practical application. The results show that, the overall thermal decomposition pathway under the experimental conditions is initiated by the proton transfer between NH4 + cation and ClO4 − anion, leading to neutral NH3 and HClO4 molecules, which are absorbed on the AP surface and then escape to the gas phase. The second important step is the homolytic cleavage of the Cl-OH bond in HClO4. The energy barrier is 67.5 kJ/mol under 620 K. Then, •OH radical and •ClO3 radical react with NH3 molecule, yielding •NH2 radical. Then the •NH2 radical react with HClO4, leading to •ClO4 radical, which reacts with NH3, leading to the oxidized species H2NO. The radical species, such as •OH, •NH2, •ClO and so on, abstract the H atom of H2NO, yielding NO. NO reacts with •OH radical, leading to NO2; NO reacts with •NH2 radical and •OH radical, leading to N2O. These products are consistent well with the experimental observations. Due to the complexity of the mechanisms, some strategies are used in this study: firstly, we concentrate on the reaction pathways of active species and the NH3 and HClO4 molecules, which exist in large amount; secondly, more reaction pathways involving the newly formed active species are considered.

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Quantum Chemical Investigation of Perchloric Acid Decomposition Releasing Oxygen

Cited by 2 publications

References 35 publications

Exploring the Correlation between Azido-Tetrazolo Tautomerizations and Isomer Structures: Electron Density of Bonding N Atoms and N–N Bond Polarity

Exploring the Correlation between Azido-Tetrazolo Tautomerizations and Isomer Structures: Electron Density of Bonding N Atoms and N–N Bond Polarity

Density Functional Theory Study on Thermal Decomposition Mechanisms of Ammonium Perchlorate

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