Pub Date : 2024-12-01DOI: 10.1016/j.enmf.2023.09.004
Zhi-xiang Zhang , Yi-lin Cao , Chao Chen , Lin-yuan Wen , Yi-ding Ma , Bo-zhou Wang , Ying-zhe Liu
In this study, machine learning (ML)-assisted regression modeling was conducted to predict the thermal decomposition temperatures and explore the factors that correlate with the thermal stability of energetic materials (EMs). The modeling was performed based on a dataset consisting of 885 various compounds using linear and nonlinear algorithms. The tree-based models established demonstrated acceptable predictive abilities, yielding a low mean absolute error (MAE) of 31°C. By analyzing the dataset through hierarchical classification, this study insightfully identified the factors affecting EMs’ thermal decomposition temperatures, with the overall accuracy improved through targeted modeling. The SHapley Additive exPlanations (SHAP) analysis indicated that descriptors such as BCUT2D, PEOE_VSA, MolLog_P, and TPSA played a significant role, demonstrating that the thermal decomposition process is influenced by multiple factors relating to the composition, electron distribution, chemical bond properties, and substituent type of molecules. Additionally, descriptors such as Carbon_contents and Oxygen_Balance proposed for characterizing EMs showed strong linear correlations with thermal decomposition temperatures. The trends of their SHAP values indicated that the most suitable ranges of Carbon_contents and Oxygen_Balance were 0.2∼0.35 and −65∼−55, respectively. Overall, the study shows the potential of ML models for decomposition temperature prediction of EMs and provides insights into the characteristics of molecular descriptors.
{"title":"Machine learning-assisted quantitative prediction of thermal decomposition temperatures of energetic materials and their thermal stability analysis","authors":"Zhi-xiang Zhang , Yi-lin Cao , Chao Chen , Lin-yuan Wen , Yi-ding Ma , Bo-zhou Wang , Ying-zhe Liu","doi":"10.1016/j.enmf.2023.09.004","DOIUrl":"10.1016/j.enmf.2023.09.004","url":null,"abstract":"<div><div>In this study, machine learning (ML)-assisted regression modeling was conducted to predict the thermal decomposition temperatures and explore the factors that correlate with the thermal stability of energetic materials (EMs). The modeling was performed based on a dataset consisting of 885 various compounds using linear and nonlinear algorithms. The tree-based models established demonstrated acceptable predictive abilities, yielding a low mean absolute error (<em>MAE</em>) of 31°C. By analyzing the dataset through hierarchical classification, this study insightfully identified the factors affecting EMs’ thermal decomposition temperatures, with the overall accuracy improved through targeted modeling. The SHapley Additive exPlanations (SHAP) analysis indicated that descriptors such as BCUT2D, PEOE_VSA, MolLog_P, and TPSA played a significant role, demonstrating that the thermal decomposition process is influenced by multiple factors relating to the composition, electron distribution, chemical bond properties, and substituent type of molecules. Additionally, descriptors such as Carbon_contents and Oxygen_Balance proposed for characterizing EMs showed strong linear correlations with thermal decomposition temperatures. The trends of their SHAP values indicated that the most suitable ranges of Carbon_contents and Oxygen_Balance were 0.2∼0.35 and −65∼−55, respectively. Overall, the study shows the potential of ML models for decomposition temperature prediction of EMs and provides insights into the characteristics of molecular descriptors.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"5 4","pages":"Pages 274-282"},"PeriodicalIF":3.3,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135348903","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-01DOI: 10.1016/j.enmf.2024.01.002
Luciana Amorim da Silva, Gabriel Monteiro-de-Castro, Erick Braga Ferrão Galante, Itamar Borges Jr, Aline Cardoso Anastácio
<div><div>The main challenge in designing new energetic materials is to find a good balance between four seemingly incompatible requirements, namely, high-energy content, low sensitivity, low production costs and less-polluting content. Fused nitrogen heterocycles of imidazole and pyrimidine, such as acyclovir and guanine, may offer interesting features due to the combination of a coplanar framework and a large conjugate system, which contribute to a reduced sensitivity, and a number of energetic bonds that can be increased by the introduction of explosophore substituents. In this work, to evaluate the potential of acyclovir and guanine derivatives as energetic materials, density functional theory (DFT) calculations were carried out to investigate the influence of the type and position of the explosophore substituent groups –<span><math><mrow><mi>N</mi><msub><mi>O</mi><mn>2</mn></msub></mrow></math></span>, –<span><math><mrow><mi>N</mi><mi>H</mi><mi>N</mi><msub><mi>O</mi><mn>2</mn></msub></mrow></math></span>, –<span><math><mrow><msub><mi>N</mi><mn>3</mn></msub></mrow></math></span>, –<span><math><mrow><mi>O</mi><mi>N</mi><msub><mi>O</mi><mn>2</mn></msub></mrow></math></span>, –<span><math><mrow><mi>C</mi><mi>N</mi></mrow></math></span>, <span><math><mrow><mo>−</mo><mi>N</mi><mo>=</mo><mi>N</mi><mo>−</mo><mtext>,</mtext></mrow></math></span> and <span><math><mrow><mo>−</mo><mi>N</mi><mo>=</mo><mi>N</mi><mrow><mo>(</mo><mi>O</mi><mo>)</mo></mrow><mo>−</mo></mrow></math></span> on the energetic properties and chemical reactivity of 91 acyclovir- and guanine-based molecules, including thirty one nitramines, three nitroheterocycles, seventeen azides, seventeen nitrate esters, seventeen nitriles, three azo and three azoxy compounds. Several molecular properties were computed, including the chemical reactivity, the heat of formation and the detonation velocities and pressures using semiempirical equations. Among the molecules with no bridge groups, we found that, except for cyano group, position 4 were the most stable for acyclovir derivatives, whereas, except for the azido group, position 2 and 5 provided the most stable compounds for guanine derivatives. Among the bridged derivatives, depending on the molecule and positions, the nitrate esters and the nitro derivatives were more stable. In comparison with the parent compounds, calculations showed that the heat of formation (HOF) increased the most with azido and cyano groups, the density increased substantially with nitrate esters, nitro and nitramino groups, and the detonation velocities and pressures increased the most with nitrate ester, nitro and nitramino groups. Although azo groups resulted in higher HOFs than azoxy groups, azoxy derivatives showed superior values in terms of density, heat of maximum detonation, detonation velocity and pressure. Four nitrate esters (GD134, GD245, AZOXYGD13 and AZOXYGD25) displayed higher values of detonation velocity and pressure than RDX. The designed nitramin
{"title":"A density functional theory investigation of the substituent effect on acyclovir and guanine derivatives for applications on energetic materials","authors":"Luciana Amorim da Silva, Gabriel Monteiro-de-Castro, Erick Braga Ferrão Galante, Itamar Borges Jr, Aline Cardoso Anastácio","doi":"10.1016/j.enmf.2024.01.002","DOIUrl":"10.1016/j.enmf.2024.01.002","url":null,"abstract":"<div><div>The main challenge in designing new energetic materials is to find a good balance between four seemingly incompatible requirements, namely, high-energy content, low sensitivity, low production costs and less-polluting content. Fused nitrogen heterocycles of imidazole and pyrimidine, such as acyclovir and guanine, may offer interesting features due to the combination of a coplanar framework and a large conjugate system, which contribute to a reduced sensitivity, and a number of energetic bonds that can be increased by the introduction of explosophore substituents. In this work, to evaluate the potential of acyclovir and guanine derivatives as energetic materials, density functional theory (DFT) calculations were carried out to investigate the influence of the type and position of the explosophore substituent groups –<span><math><mrow><mi>N</mi><msub><mi>O</mi><mn>2</mn></msub></mrow></math></span>, –<span><math><mrow><mi>N</mi><mi>H</mi><mi>N</mi><msub><mi>O</mi><mn>2</mn></msub></mrow></math></span>, –<span><math><mrow><msub><mi>N</mi><mn>3</mn></msub></mrow></math></span>, –<span><math><mrow><mi>O</mi><mi>N</mi><msub><mi>O</mi><mn>2</mn></msub></mrow></math></span>, –<span><math><mrow><mi>C</mi><mi>N</mi></mrow></math></span>, <span><math><mrow><mo>−</mo><mi>N</mi><mo>=</mo><mi>N</mi><mo>−</mo><mtext>,</mtext></mrow></math></span> and <span><math><mrow><mo>−</mo><mi>N</mi><mo>=</mo><mi>N</mi><mrow><mo>(</mo><mi>O</mi><mo>)</mo></mrow><mo>−</mo></mrow></math></span> on the energetic properties and chemical reactivity of 91 acyclovir- and guanine-based molecules, including thirty one nitramines, three nitroheterocycles, seventeen azides, seventeen nitrate esters, seventeen nitriles, three azo and three azoxy compounds. Several molecular properties were computed, including the chemical reactivity, the heat of formation and the detonation velocities and pressures using semiempirical equations. Among the molecules with no bridge groups, we found that, except for cyano group, position 4 were the most stable for acyclovir derivatives, whereas, except for the azido group, position 2 and 5 provided the most stable compounds for guanine derivatives. Among the bridged derivatives, depending on the molecule and positions, the nitrate esters and the nitro derivatives were more stable. In comparison with the parent compounds, calculations showed that the heat of formation (HOF) increased the most with azido and cyano groups, the density increased substantially with nitrate esters, nitro and nitramino groups, and the detonation velocities and pressures increased the most with nitrate ester, nitro and nitramino groups. Although azo groups resulted in higher HOFs than azoxy groups, azoxy derivatives showed superior values in terms of density, heat of maximum detonation, detonation velocity and pressure. Four nitrate esters (GD134, GD245, AZOXYGD13 and AZOXYGD25) displayed higher values of detonation velocity and pressure than RDX. The designed nitramin","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"5 4","pages":"Pages 293-308"},"PeriodicalIF":3.3,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139952275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-01DOI: 10.1016/j.enmf.2024.07.001
Guan-chen Dong , Jia-lu Guan , Ling-hua Tan , Jing Lv , Xiao-na Huang , Guang-cheng Yang
1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) is a highly insensitive energetic material used in applications where extreme safety is required primarily. Ensuring the safe use of TATB as planned relies on research into intrinsic behavior under shock loading, which needs further investigation. Here, we study the shock response in oriented supercells of the highly anisotropic TATB based on reactive molecular dynamics simulations and multi-scale shock technique. Results demonstrate that the mechanical response primarily consists of adiabatic compression and plastic deformation. The system is more susceptible to be compressed rather than plastic deformed when shocked direction to the molecular layer at a 45° angle, resulting in the most obvious initial temperature increase. The chemical reaction pathways are similar in our simulations. Under shock loading, polymerization occurs first and then decomposition begins. However, the overall chemical kinetics response intensifies, as the angle between the shock direction and molecular layer decreases. Nonetheless, the rate of decomposition does not strictly correlate with shock direction. Moreover, clusters evolution shows different reactivity based on shock direction and velocity, which makes anisotropy weak at high shock velocity.
{"title":"Anisotropic shock response in oriented omnidirectional TATB supercells based on reactive molecular dynamics simulations","authors":"Guan-chen Dong , Jia-lu Guan , Ling-hua Tan , Jing Lv , Xiao-na Huang , Guang-cheng Yang","doi":"10.1016/j.enmf.2024.07.001","DOIUrl":"10.1016/j.enmf.2024.07.001","url":null,"abstract":"<div><div>1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) is a highly insensitive energetic material used in applications where extreme safety is required primarily. Ensuring the safe use of TATB as planned relies on research into intrinsic behavior under shock loading, which needs further investigation. Here, we study the shock response in oriented supercells of the highly anisotropic TATB based on reactive molecular dynamics simulations and multi-scale shock technique. Results demonstrate that the mechanical response primarily consists of adiabatic compression and plastic deformation. The system is more susceptible to be compressed rather than plastic deformed when shocked direction to the molecular layer at a 45° angle, resulting in the most obvious initial temperature increase. The chemical reaction pathways are similar in our simulations. Under shock loading, polymerization occurs first and then decomposition begins. However, the overall chemical kinetics response intensifies, as the angle between the shock direction and molecular layer decreases. Nonetheless, the rate of decomposition does not strictly correlate with shock direction. Moreover, clusters evolution shows different reactivity based on shock direction and velocity, which makes anisotropy weak at high shock velocity.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"5 4","pages":"Pages 318-328"},"PeriodicalIF":3.3,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141770485","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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