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<p>The energetic properties of high-energy molecules are significantly influenced by structural modifications, especially the positional arrangement of functional groups such as nitro and nitramine. Understanding these structural effects is crucial for designing more efficient energetic materials. In this study, Density Functional Theory (DFT) calculations at the M06-2X/6–311 +  + G** level were employed to investigate the influence of the positional arrangement of nitro and nitramine groups on the energetic characteristics of six high-energy molecules. Thermodynamic parameters, including heat of formation (HOF), bond dissociation energy (BDE), and impact sensitivity indices, were systematically evaluated. Additionally, detonation properties such as detonation velocity (D) and pressure (P) were calculated and analyzed. N–NO₂ bonds were found to have systematically lower BDEs than C–NO<sub>2</sub> bonds, identifying N–NO<sub>2</sub> cleavage as the primary initiation channel for thermal decomposition. Detonation properties (Q, D, and P) were evaluated via the Kamlet–Jacobs relations. R4 and R6 have the highest detonation velocities and pressures (D ≈ 8.36 and 8.35&#xa0;km·s⁻<sup>1</sup>; <i>P</i> ≈ 30.8 and 31.3&#xa0;GPa), whereas R5 shows the lowest performance (D = 6.99&#xa0;km·s⁻<sup>1</sup>, <i>P</i> = 18.49&#xa0;GPa). Analysis shows that electron-withdrawing nitro/nitramine groups tend to raise HOF, methyl substitution slightly lowers both HOF and detonation metrics via electron donation, and substituent positioning (structural isomerism) led to notable differences in BDE and detonation behavior despite identical molecular formulas, underscoring the critical role of substituent positioning. These results provide quantitative structure–property guidance for designing nitramine-based high-energy materials with balanced performance and thermal stability.</p>

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Positional effects of nitro and nitramine groups in cyclic energetic molecules: a DFT-based stability and performance analysis

  • 期刊论文

  • 发表日期：

    2025年12月15日

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  • Davood Farmanzadeh,
  • Aleme Rasouli,
  • Roudabeh Mohsseni Ahangar,
  • Effat Kianpouur,
  • Fatemeh Fateminasab

摘要

The energetic properties of high-energy molecules are significantly influenced by structural modifications, especially the positional arrangement of functional groups such as nitro and nitramine. Understanding these structural effects is crucial for designing more efficient energetic materials. In this study, Density Functional Theory (DFT) calculations at the M06-2X/6–311 +  + G** level were employed to investigate the influence of the positional arrangement of nitro and nitramine groups on the energetic characteristics of six high-energy molecules. Thermodynamic parameters, including heat of formation (HOF), bond dissociation energy (BDE), and impact sensitivity indices, were systematically evaluated. Additionally, detonation properties such as detonation velocity (D) and pressure (P) were calculated and analyzed. N–NO₂ bonds were found to have systematically lower BDEs than C–NO2 bonds, identifying N–NO2 cleavage as the primary initiation channel for thermal decomposition. Detonation properties (Q, D, and P) were evaluated via the Kamlet–Jacobs relations. R4 and R6 have the highest detonation velocities and pressures (D ≈ 8.36 and 8.35 km·s⁻1; P ≈ 30.8 and 31.3 GPa), whereas R5 shows the lowest performance (D = 6.99 km·s⁻1, P = 18.49 GPa). Analysis shows that electron-withdrawing nitro/nitramine groups tend to raise HOF, methyl substitution slightly lowers both HOF and detonation metrics via electron donation, and substituent positioning (structural isomerism) led to notable differences in BDE and detonation behavior despite identical molecular formulas, underscoring the critical role of substituent positioning. These results provide quantitative structure–property guidance for designing nitramine-based high-energy materials with balanced performance and thermal stability.