Molecular Dynamic Simulation Study on the Influence of Heating Rate on the Thermal Decomposition Process of 1,3,5-Triamino- 2,4,6-Trinitrobenzene (TATB)

Molecular Dynamic Simulation Study on the Influence of Heating Rate on the Thermal Decomposition Process of 1,3,5-Triamino- 2,4,6-Trinitrobenzene (TATB) | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Molecular Dynamic Simulation Study on the Influence of Heating Rate on the Thermal Decomposition Process of 1,3,5-Triamino- 2,4,6-Trinitrobenzene (TATB) Xianfeng Wei, Shan Sha, Qingying Duan This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5457870/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 14 Jan, 2025 Read the published version in Journal of Molecular Modeling → Version 1 posted 10 You are reading this latest preprint version Abstract To clarify the effect of heating rate on the thermal decomposition process of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), this study employs molecular dynamic simulations to investigate the thermal decomposition of TATB at heating rates of 20, 40, 60, and 80 K/ps. The initial temperature is uniformly set to 300 K, while the final temperature is set to 3000 K. Results indicate that within the temperature range of 300–3000 K, the thermal decomposition rate of TATB decreases with increasing heating rate, whereas the initial decomposition temperature of TATB increases, consistent with the experimental pattern. Within the studied temperature range, a lower heating rate results in a longer decomposition time, leading to increased collision reaction time of decomposition products, a higher probability of formation, and more stable products, such as H 2 O, CO 2 , and N 2 . Conversely, at higher heating rates, the quantities of H 2 O, CO 2 , and N 2 are reduced. Methods： The Gaussian09 software was used to calculate the BDEs of TATB molecules, while the MD simulation was performed using the LAMMPS package. Visualization and postprocessing were conducted using the OVITO software, and a custom script was developed to analyze the reaction products and frequencies. Energetic material Thermal decomposition Reactive molecular dynamics Decomposition products Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 1. Introduction 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) is a high-energy and low-sensitivity explosive known for its insensitivity to shock stimuli and high temperatures, as well as its excellent detonation performance. Owing to its superior safety, it is often referred to as “wood explosive” [1]. TATB is commonly used in cocrystals with powerful explosives, such as 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), to reduce sensitivity [2,3]. Current research on TATB mainly focuses on its improvements in crystallization techniques, shock sensitivity, coating for sensitivity reduction, crystal stability, the effect of defects on sensitivity, and interfacial interactions in solutions [4–11]. TATB crystals possess a unique layered structure similar to graphite, allowing them to dissipate impact energy through interlayer sliding, which results in a high impact sensitivity parameter (H 50 ) of up to 320 cm [12,13], indicating very low sensitivity. In addition to its excellent impact sensitivity, TATB also exhibits low sensitivity to high temperatures, with a thermal decomposition temperature reaching 350°C [14]. Thermal decomposition temperature is a critical standard for evaluating the safety of explosives. The higher the decomposition temperature, the better the safety performance. However, because of the influence of testing conditions and different heating rates, this temperature is not a fixed value for energetic materials (EMs). Experimental results for various EMs, such as 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), CL-20, HMX, and TATB, indicate that their thermal decomposition temperatures increase with rising heating rates [15–18]. The heating rate significantly affects the thermal decomposition temperature of EMs, and the underlying reasons for this influence warrant further investigation. This study focuses on TATB, conducting molecular dynamic (MD) research on its thermal decomposition process. The decomposition products and formation processes at different heating rates are analyzed, aiming to elucidate the reasons behind the effect of heating rate on thermal decomposition temperature. This study establishes a uniform heating range (300–3000 K) and evaluates the thermal decomposition process and products of TATB at heating rates of 20, 40, 60, and 80 K/ps. It contributes to an enhanced understanding of TATB’s thermal decomposition mechanism, providing a reference for its safe usage. 2. Computational Procedure and Methods In this study, the Becke 3-parameter, Lee–Yang–Parr method under the density functional theory framework was employed for the structural optimization of TATB molecules and their related molecular groups using the 6-31G(d,p) basis set. Energy calculations were performed with the cc-pVTZ basis set to determine the bond dissociation energies (BDEs) of C-NO 2 , C-NH 2 , N-H, and N-O within the molecule. A 4×4×4 TATB supercell model (Fig. 1 ) was constructed using the TATB unit cell (CCDC: 1266837). The unit cell parameters of TATB were as follows: a = 9.01 Å, b = 9.028 Å, c = 6.812 Å, α = 108.58°, β = 91.82°, γ = 119.97°, and space group Pī. Each unit cell contained two TATB molecules [19], and the constructed supercell model consisted of 128 TATB molecules. Given that periodic boundary conditions were applied during the simulation, the TATB model could expand periodically in three dimensions, effectively representing a bulk-scale TATB crystal. MD simulations were conducted on the TATB supercell model using the ReaxFF-lg reactive force field. Numerous studies have previously validated the successful application of the ReaxFF-lg force field in simulating the performance of TATB under shock loading conditions [12], so its suitability was not reverified here. For investigating the relationship between the degree of thermal decomposition of TATB and heating rate, heating simulations were performed on the model at rates of 20, 40, 60, and 80 K/ps. First, energy minimization was performed on the constructed model, followed by 5 ps of isothermal–isobaric (NPT) relaxation at 300 K. Subsequently, canonical ensemble (NVT) dynamics were employed to heat the model continuously from 300 K to 3000 K at heating rates of 20, 40, 60, and 80 K/ps. The time step was set to 0.1 fs, and dynamic trajectories were recorded every 1000 steps. In MD simulations of the thermal decomposition of EMs, heating rates ranging from 0 K/ps to 100 K/ps are commonly used. Although these rates are significantly higher than the 10 − 3 –10 K/ps rates used in experiments, numerous theoretical studies have demonstrated that such differences in heating rates do not affect the investigation of chemical reaction mechanisms during decomposition [20]. In this study, the Gaussian09 software [21] was used to calculate the BDEs of TATB molecules, while the MD simulation was performed using the LAMMPS package [22]. Visualization and postprocessing were conducted using the OVITO software [23], and a custom script was developed to analyze the reaction products and frequencies. 3. Results and Analysis 3.1 Structural Analysis of TATB Molecules Table 1 BDEs of C-NO 2 , C-NH 2 , N-H, and N-O in TATB molecules Bond Type BDE (KJ/mol) C-NO 2 293.18 C-NH 2 462.92 N-H 480.27 N-O 607.07 Table 1 presents the BDEs of C-NO 2 , C-NH 2 , N-H, and N-O in TATB molecules after optimization. The BDE of C-NO 2 is much lower than those of C-NH 2 , N-H, and N-O. These BDE values indicate that the C-NO 2 bond is more likely to break in a single molecule. 3.2 MD Study of TATB Thermal Decomposition Figure 2 illustrates the variation in the number of TATB molecules with temperature at different heating rates. At all four heating rates, no significant decomposition of TATB occurs before the temperature reaches 1000 K. In the 300–3000 K temperature range, the decomposition rate of TATB decreases as the heating rate increases. When the heating rate is 20 K/ps, the decomposition rate of TATB is more pronounced, while the differences between 60 and 80 K/ps are not significant. Table 2 DSC test values and MD simulation values of TATB at different heating rates MD Simulation Values Experimental Values Heating Rate (K/ps) Initial Decomposition Temperature K (T ical ) Heating Rate (K*min − 1 ) Initial Decomposition Temperature (T i ) Peak Temperature (T p ) 20 1200 5 642.43 K 644.83 K 40 1700 10 654.84 K 656.38 K 60 1800 15 661.51 K 663.83 K 80 1900 20 666.05 K 669.01 K The simulation results show that when the temperature reaches 3000 K, TATB does not fully decompose into stable products such as H 2 O, CO 2 , and N 2 ; instead, a large number of clusters are formed. Therefore, the simulation cannot determine a peak temperature (T pcal ) under 3000 K. Nevertheless, the simulation results indicate that the initial decomposition temperature (T ical ) increases with rising heating rates, as shown in Table 2 . The differential scanning calorimetry (DSC) experimental results of TATB at different heating rates [24] also show that the initial decomposition temperature (T i ) and peak temperature (T p ) increase with higher heating rates, which is consistent with the theoretical trends. The studies on TATB decomposition under high pressure have shown that pressure increases TATB’s stability, hindering its thermal decomposition; the higher the pressure, the more significant this effect [14]. In this simulation, the volume of the TATB model remains constant, and as the temperature increases, internal pressure builds up. The higher the heating rate is, the faster the internal pressure rises, leading to increases in T ical and T zcal . The simulation results of this study support the findings from high-pressure TATB decomposition studies and align with experimental observations. Because the final temperature was set to 3000 K for all simulations, the duration of the simulations differed depending on the heating rate. Figure 3 illustrates the time-dependent variation in the quantities of the primary free radicals generated during the thermal decomposition of TATB. At all four heating rates, the radicals − H and − O are the first to appear, whereas − HO and − NO 2 emerge later. This finding suggests that the detachment of hydrogen atoms from the − NH 2 groups is likely the first step in the decomposition of TATB molecules, followed by the detachment of oxygen atoms from the − NO 2 groups. According to the BDE data of static TATB molecules (Table 1 ), −NO 2 is the easiest bond to break. However, in the crystal model, −H breaks first, indicating a discrepancy between the molecular and crystal models. This difference arises because intermolecular interactions and packing arrangements in the crystal structure influence the bonding behavior of TATB molecules and, consequently, affect the bond dissociation process. Figure 4 shows the inferred initial decomposition reactions of TATB crystals based on the time-dependent changes in the quantities of decomposition products during heating. Reactions II and III appear early in the decomposition process and result in substantial decomposition. Both reactions, along with subsequent reactions, generate − H and − O, which later combine to form − HO. Reaction I , which involves intramolecular hydrogen transfer, also produces − HO. During the early stages of heating, the energy supplied to the TATB crystal from external sources is insufficient to drive Reactions II and III extensively because these reactions require more energy. By contrast, Reaction I requires less energy and is easier to initiate. Therefore, Reaction I is likely to occur earlier than Reactions II and III . Figure 5 shows the temperature-dependent variations in the quantities of the same free radicals at different heating rates. For the primary ions produced during decomposition, such as − H, −O, −HO, −NO 2 , and − NO, the trends in quantity changes are consistent across different heating rates. As the heating rate increases, the temperature at which these free radicals first appear also rises. This behavior of the primary free radical products aligns with the relationship between heating rate and decomposition rate, in which higher heating rates result in slower TATB decomposition. Based on Figs. 3 and 6 , as − H appears, the structure C 6 H 7 O 6 N 6 forms after a prolonged heating period, indicating that intermolecular hydrogen transfer occurs during TATB decomposition. Figure 6 highlights the peak temperatures corresponding to the maximum quantities of C 6 H 7 O 6 N 6 structures at different heating rates: 1840 K (20 K/ps), 1980 K (40 K/ps), 2020 K (60 K/ps), and 2380 K (80 K/ps). They are situated between the initial decomposition temperature T ical and the temperature at which the TATB molecule count reaches zero T zcal . As shown in Fig. 3 , the quantity of − HO increases steadily in the later stages of heating at all four heating rates, but it does not exceed the quantities formed in the early stages. The trends in C 6 H 7 O 6 N 6 structure formation in Fig. 6 , along with the reaction pathways illustrated in Fig. 4 , indicate that − HO formation in the thermal decomposition process of TATB originates from two possible pathways. In the early stages, −HO is produced through intramolecular hydrogen transfer and the detachment of H and O atoms from − NH 2 and − NO 2 groups on the TATB molecule. In the later stages, −HO is formed through intermolecular hydrogen transfer and subsequent detachment. This section analyzes the three primary stable products (H₂O, CO₂, and N₂) generated during the thermal decomposition of TATB. Figure 7 presents the time-dependent variations in the quantities of these stable products. At all four heating rates, H₂O is the first stable product to form. Overall, as temperature increases, the quantities of H₂O, CO₂, and N₂ also increase across different heating rates. In Fig. 7 a, at a heating rate of 20 K/ps, the quantity of H₂O tends to stabilize at around 2600 K. In Fig. 7 b, at a heating rate of 40 K/ps, the quantity of H₂O stabilizes at around 3000 K; at heating rates of 60 and 80 K/ps, the quantity of H₂O continues to increase. Similar trends are observed for N₂ in Fig. 7 a, in which the quantity of N₂ tends to stabilize at around 2800 K at a heating rate of 20 K/ps. For the 40 K/ps heating rate, N₂ stabilizes at 3000 K. By contrast, the quantity of N₂ continues to increase at heating rates of 60 and 80 K/ps. As for CO₂, it forms after the breakdown of the six-membered carbon ring, which occurs later in the thermal decomposition process of TATB. Therefore, as noted earlier, with a maximum temperature setting of 3000 K, the higher the heating rate, the slower the decomposition rate, and the shorter the duration of the heating process. This condition reduces the time available for free radicals to collide and react, thereby limiting the formation of CO₂. Consequently, the quantity of CO₂ only increases during the later stages of thermal decomposition. This analysis suggests that at 3000 K, the decomposition of TATB within the model is incomplete. Figure 8 compares the temperature-dependent variations in the quantities of the same decomposition products at different heating rates. Because of the pressure within the system inhibiting the decomposition process, higher heating rates result in slower decomposition. Consequently, at the same temperature, the quantities of H₂O, N₂, and CO₂ decrease as the heating rate increases. When the heating rate is faster, free radicals in the model do not have enough time to collide and form stable products, leading to fewer decomposition products. Within the 300–3000 K temperature range, N₂ is the second most abundant final product after H₂O. The formation of N₂ is dependent on the generation of − NH and − NO radicals. Therefore, at higher heating rates, the increased pressure in the simulation system suppresses the formation of − NH and − NO, reducing the quantity of N₂ and delaying its appearance (Fig. 3 ). At a heating rate of 20 K/ps, however, the final quantity of N₂ surpasses that of H₂O (Fig. 7 a), which is consistent with the literature [14], that is, the generation of N₂ is accompanied with a reduction in H₂O during TATB thermal decomposition. In theoretical simulations, a heating rate of 20 K/ps allows enough time for the free radicals generated during TATB decomposition to fully react, thereby balancing the decomposition rate with the product formation rate. When higher heating rates (40, 60, and 80 K/ps) are used, a higher cutoff temperature is needed to extend the reaction time, allowing sufficient time for free radicals to fully react. Based on the simulation results in this study, when conducting simulations of EMs’ thermal decomposition, lower heating rates should be used to observe complete reactions if the temperature is set lower, while higher heating rates require a corresponding increase in the cutoff temperature. According to the maximum heat release principle, during a DSC test, the maximum exothermic point for EMs is reached when the quantities of H₂O and CO₂ reach their peaks, corresponding to the thermal decomposition peak temperature T p . However, in this simulation, because the cutoff temperature is set to 3000 K, the decomposition process of TATB is not fully completed, preventing the determination of the simulated peak temperature T pcal . As the heating rate increases, the quantities of H₂O, CO₂, and N₂ decrease (Fig. 8 ), which contradicts the maximum heat release principle. This discrepancy is due to the limitation imposed by the temperature range set in this study. For calculating the variation in T pcal with heating rate, the final temperature should be increased in the simulation. The temperature at which the number of TATB molecules reaches zero T zcal shows an upward trend with increasing heating rates, which also does not align with the maximum heat release principle. The reason is that the TATB model used in this study is a crystal model. Moreover, when the NVT ensemble is employed, the entire model remains in an overpressure state once heating begins. As a result, it is difficult for H₂O, CO₂, and N₂ to exist in gaseous form, making the quantities of these decomposition products inaccurate indicators of T zcal variations across different heating rates. To address this issue, this study tracks the total quantity of internal compounds and fragments in the model as a function of temperature, as shown in Fig. 9 . Under the same temperature conditions, the higher the heating rate, the fewer internal compounds and fragments form within the 300–3000 K range. This trend is consistent with the variation in the quantities of H₂O, CO₂, and N₂. 4. Conclusion Within the same temperature range (300–3000 K), the heating rate does not affect the thermal decomposition mechanism of TATB. According to the analysis in this study, the formation of − HO during TATB decomposition occurs via three pathways: (1) intramolecular hydrogen transfer followed by the detachment of − HO in the early stages of the reaction, (2) the detachment of H and O from − NH₂ and − NO₂ groups in TATB to form − HO, and (3) intermolecular hydrogen transfer leading to the release of − HO in the later stages of decomposition. In the studied temperature range, the decomposition rate of TATB decreases as the heating rate increases because of the pressure within the simulation system. The initial decomposition temperature of TATB rises with higher heating rates. The heating rate also influences the quantity of decomposition products, particularly those formed in the later stages. The simulation results demonstrate that at lower heating rates, the decomposition process takes longer, allowing more time for collisions between decomposition products and increasing the probability of their combination. As a result, more stable products, such as H₂O, CO₂, and N₂, are formed. Conversely, at higher heating rates, fewer H₂O, CO₂, and N₂ molecules are produced. Declarations Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Author Contribution Xianfeng Wei: Wrote the main manuscript, Investigation, review & editing, Supervision, Methodology, Funding acquisition.Shan Sha: Investigation, Data curation. Qingying Duan: Investigation, Data curation. Acknowledgements The authors gratefully acknowledge the support of NSFC (22173086). References Slape R J (1984) IHE material qualifcation tests description and criteria, 1984. Xu H, Duan X, Li H, Pei C (2015) A novel high-energetic and good-sensitive cocrystal composed of CL-20 and TATB by a rapid solvent/non-solvent method. RSC Adv. 5:95764. Hou C, Liu Z, Zhang Y, Chen Y, Zhang S (2017). Study on preparation and properties of TATB/HMX cocrystal explosive. Chinese Journal of Explosive & Propellants. 40(4):6. Wang Y, Wang B, Ye Z, Shang Y, Qing H, Li Y (2011) Synthesis of TATB by VNS method. Chin. J. Energ. Mater. 19(2):142-146. Zhang C, Jiao F, Li H (2018), Crystal Engineering for Creating Low Sensitivity and Highly Energetic Materials, Cryst. Growth Des. 18:5713-5726. Huang B, Cao M, Wu X, Nie F, Huang H, Hu C (2011) Twinned TATB nanobelts: synthesis, characterization, and formation mechanism. CrystEngComm. 13: 6658-6664. Xiong X, He X, Xiong Y, Xue X, Yang H, Zhang C (2020) Correlation between the self-sustaining ignition ability and the impact sensitivity of energetic materials, Energ. Mater. Front. 1:40-49. Zuo C, Zhang C (2024) 1,3,5-Triamino-2,4,6-Trinitrobenzene (TATB): Enlightening the way to create new Low-Sensitivity and High-Energy materials from a viewpoint of multiscale. Chem. Eng. J. 490:151737. Ma Y, Zhang A, Zhang C, Jiang D, Zhu Y, Zhang C (2014) Crystal packing of low-sensitivity and high-energy explosives. Cryst. Growth Des. 14(9):4703-4713. Zhong K, Bu R, Jiao F, Liu G, Zhang C (2022) Toward the defect engineering of energetic materials: A review of the effect of crystal defects on the sensitivity, Chem. Eng. J. 429:132310. Wang L, Chen D, Li H, Duan X, Yu Y (2020) Crystal morphology of β-HMX under eight solvents system using molecular dynamics simulation and experiment. Chin. J. Energ. Mater. 28(4):317-329. Zhou T, Song H, Huang F (2017) The Slip and Anisotropy of TATB Crystal under Shock Loading via Molecular Dynamics Simulation. Acta Phys. -Chim. Sin. 33(5):949-959. Roman T, Onise S, Maija K (2016) Molecular theory of detonation initiation: Insight from first principles modeling of the decomposition mechanisms of organic nitro energetic materials. Molecules. 21(2):236. Sun X, Liang W, Li X, Gao C, Dai R, Wang Z, Zhang Z (2022) Advances of high-temperature and high-pressure physical properties and experimental technology on high-energy insensitive explosive TATB. Chin. J. of High-Pressure Phys. 36(3):030101. Ding Y, Wu Y, Wang H, Liu G, Ji W (2014) Effects of TNT on the thermal decomposition performance of RDX. Exp. Mater. 43(05):21-25. Liu J, Zhao N, Zhao F, Song J, Ma H (2015) Preparation of sea urchin-shaped nano-MnO 2 and its effect on thermal decomposition performance of CL-20. Chin. J. Explos. Propell. 02:27-32+42. Zhang T, Guo Y, Li Y, Guo Z, Ma H (2019) Effect of nitrogen-doped graphene oxide on thermal decomposition of HMX. Chin. J. Explos. Propell. 42(04):346-351. Cao X, Luo S, Xu L, Meng R (2016) Thermal decomposition of TATB and its thermal explosion characteristics in [Emim] Ac/DMSO solvent. Chin. J. Explos. Propell. 039(001):52-55. Howard H C and Allen C L (1965) The crystal structure of 1,3,5-triamino-2,4,6-trinitrobenzene. Acta Crystallographica, 18: 485. Deng C, Xue X, Chi Y, Li H, Long X, Zhang C (2017) Nature of the enhanced self-heating ability of imperfect energetic crystals relative to perfect ones. J. Phys. Chem. C. 121:12101−12109. Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Scalmani G, Barone V, Mennucci B, Petersson G A (2010) Gaussian 09, Revision B.01. Gaussian Inc., Wallingford. Plimpton S (1995) Fast Parallel Algorithms for Short-Range Molecular Dynamics, J. Comput. Phys. 117(1):1-19. Stukowski A (2010) Visualization and analysis of atomistic simulation data with OVITO-the Open Visualization Tool, Modelling Simul. Mater. Sci. Eng. 18:015012. Li P, Aodeng G, Li C, Duan X, Pei C (2019) Construction and thermal decomposition kinetics of the keel-like nanostructure TATB. Chin. J. Energ. Mater. 27(02):137-143. Additional Declarations No competing interests reported. Cite Share Download PDF Status: Published Journal Publication published 14 Jan, 2025 Read the published version in Journal of Molecular Modeling → Version 1 posted Editorial decision: Revision requested 28 Nov, 2024 Reviews received at journal 28 Nov, 2024 Reviewers agreed at journal 24 Nov, 2024 Reviews received at journal 21 Nov, 2024 Reviewers agreed at journal 20 Nov, 2024 Reviewers agreed at journal 20 Nov, 2024 Reviewers invited by journal 20 Nov, 2024 Editor assigned by journal 20 Nov, 2024 Submission checks completed at journal 20 Nov, 2024 First submitted to journal 15 Nov, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-5457870","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":383816820,"identity":"f1119fb5-3a53-408e-99b2-bc8e485b9871","order_by":0,"name":"Xianfeng Wei","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAqElEQVRIiWNgGAWjYPACCTk29uYDpGkx5uM5lkCaNYnzJHIUiFNqcLv54G2eCov0NoYcBoYfFduI0HLnWLI1zxmJ3DaGswcYe87cJkLLjRwz6dw2oBbGvgRmxjaitfyTSGdj5jEgRUuDRAIbG7FaJG+kJVv/OSZh2MbDlnCQKL/w3Ug+eHNGTZ28/PzHBx/8qCBCCwhIwBgHiFOPrGUUjIJRMApGAVYAANKTN3KYPvy3AAAAAElFTkSuQmCC","orcid":"","institution":"Southwest University of Science and Technology，Mianyang","correspondingAuthor":true,"prefix":"","firstName":"Xianfeng","middleName":"","lastName":"Wei","suffix":""},{"id":383816822,"identity":"9943daab-3127-42e9-8a55-78a07909c26e","order_by":1,"name":"Shan Sha","email":"","orcid":"","institution":"Southwest University of Science and Technology，Mianyang","correspondingAuthor":false,"prefix":"","firstName":"Shan","middleName":"","lastName":"Sha","suffix":""},{"id":383816823,"identity":"ff470263-e7f7-4172-82a0-8dcf3388a46d","order_by":2,"name":"Qingying Duan","email":"","orcid":"","institution":"Southwest University of Science and Technology，Mianyang","correspondingAuthor":false,"prefix":"","firstName":"Qingying","middleName":"","lastName":"Duan","suffix":""}],"badges":[],"createdAt":"2024-11-15 05:53:19","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5457870/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5457870/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s00894-024-06270-y","type":"published","date":"2025-01-14T15:57:36+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":70455655,"identity":"8ff94377-666b-4dd0-8599-967e95cde553","added_by":"auto","created_at":"2024-12-03 10:34:46","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":83183,"visible":true,"origin":"","legend":"\u003cp\u003eTATB Supercell Model (C: Gray; H: white; N: blue; O: red)\u003c/p\u003e","description":"","filename":"1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5457870/v1/19efe98f685c9737d468b130.jpg"},{"id":70455654,"identity":"b11d15ee-0671-423b-b114-3f70cc392b54","added_by":"auto","created_at":"2024-12-03 10:34:46","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":54331,"visible":true,"origin":"","legend":"\u003cp\u003eVariation in the Number of TATB Molecules with Temperature at Different Heating Rates\u003c/p\u003e","description":"","filename":"2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5457870/v1/87c1bf01b8f7ab535324f2b3.jpg"},{"id":70455662,"identity":"253c56b6-98c4-4eaa-af94-045d2b07aba4","added_by":"auto","created_at":"2024-12-03 10:34:49","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":94385,"visible":true,"origin":"","legend":"\u003cp\u003eVariation in Major Free Radical Quantities During Simulations at Different Heating Rates\u003c/p\u003e","description":"","filename":"3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5457870/v1/2fc74b51f6ac5cca28d3c4d7.jpg"},{"id":70455656,"identity":"f03ea58b-c312-42b1-8106-3973c6f681ab","added_by":"auto","created_at":"2024-12-03 10:34:46","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":45908,"visible":true,"origin":"","legend":"\u003cp\u003eInitial Decomposition Reactions of TATB During Simulations\u003c/p\u003e","description":"","filename":"4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5457870/v1/e69129deb97fc537af726790.jpg"},{"id":70456862,"identity":"8b52df1b-af92-4e88-9456-b0dac11d5fcf","added_by":"auto","created_at":"2024-12-03 10:42:46","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":267921,"visible":true,"origin":"","legend":"\u003cp\u003eComparison of Free Radical Quantities at Different Heating Rates\u003c/p\u003e","description":"","filename":"5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5457870/v1/a80a5f70b1d9d07b9723df52.jpg"},{"id":70455663,"identity":"97ee11af-16af-4f1c-bfbb-ad5bad01d873","added_by":"auto","created_at":"2024-12-03 10:34:49","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":48432,"visible":true,"origin":"","legend":"\u003cp\u003eChanges in C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e7\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eN\u003csub\u003e6 \u003c/sub\u003eQuantities at Different Heating Rates\u003c/p\u003e","description":"","filename":"6.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5457870/v1/06ffd16dd35488a72ec7f79e.jpg"},{"id":70455659,"identity":"2bafe7d9-0274-430b-82f4-12de1670f345","added_by":"auto","created_at":"2024-12-03 10:34:46","extension":"jpg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":77285,"visible":true,"origin":"","legend":"\u003cp\u003eChanges in the Quantities of Decomposition Products (H₂O, N₂, CO₂) at Different Heating Rates\u003c/p\u003e","description":"","filename":"7.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5457870/v1/a44ca9450958318b52fd9844.jpg"},{"id":70455657,"identity":"51af9d18-5e9d-4e18-b539-ab4e67ea48d9","added_by":"auto","created_at":"2024-12-03 10:34:46","extension":"jpg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":59843,"visible":true,"origin":"","legend":"\u003cp\u003eTrends in the Quantities of H₂O, N₂, and CO₂ at Different Heating Rates\u003c/p\u003e","description":"","filename":"8.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5457870/v1/80d904c0c86123dc0615e52d.jpg"},{"id":70455660,"identity":"1c368a4c-fc27-4b8d-abc7-3f096c5a8b47","added_by":"auto","created_at":"2024-12-03 10:34:46","extension":"jpg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":49263,"visible":true,"origin":"","legend":"\u003cp\u003eTrends of the Total Quantity of Decomposition Fragments at Different Heating Rates\u003c/p\u003e","description":"","filename":"9.jpg","url":"https://assets-eu.researchsquare.com/files/rs-5457870/v1/093c453de96ba02175b60417.jpg"},{"id":74284844,"identity":"9b83ff22-06c9-445d-854e-a07a8fde193a","added_by":"auto","created_at":"2025-01-20 16:13:00","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1360664,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5457870/v1/b111407a-946f-4e8d-a66c-b3c9206474ce.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Molecular Dynamic Simulation Study on the Influence of Heating Rate on the Thermal Decomposition Process of 1,3,5-Triamino- 2,4,6-Trinitrobenzene (TATB)","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003e1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) is a high-energy and low-sensitivity explosive known for its insensitivity to shock stimuli and high temperatures, as well as its excellent detonation performance. Owing to its superior safety, it is often referred to as \u0026ldquo;wood explosive\u0026rdquo; [1]. TATB is commonly used in cocrystals with powerful explosives, such as 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), to reduce sensitivity [2,3].\u003c/p\u003e \u003cp\u003eCurrent research on TATB mainly focuses on its improvements in crystallization techniques, shock sensitivity, coating for sensitivity reduction, crystal stability, the effect of defects on sensitivity, and interfacial interactions in solutions [4\u0026ndash;11]. TATB crystals possess a unique layered structure similar to graphite, allowing them to dissipate impact energy through interlayer sliding, which results in a high impact sensitivity parameter (H\u003csub\u003e50\u003c/sub\u003e) of up to 320 cm [12,13], indicating very low sensitivity. In addition to its excellent impact sensitivity, TATB also exhibits low sensitivity to high temperatures, with a thermal decomposition temperature reaching 350\u0026deg;C [14].\u003c/p\u003e \u003cp\u003eThermal decomposition temperature is a critical standard for evaluating the safety of explosives. The higher the decomposition temperature, the better the safety performance. However, because of the influence of testing conditions and different heating rates, this temperature is not a fixed value for energetic materials (EMs). Experimental results for various EMs, such as 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), CL-20, HMX, and TATB, indicate that their thermal decomposition temperatures increase with rising heating rates [15\u0026ndash;18]. The heating rate significantly affects the thermal decomposition temperature of EMs, and the underlying reasons for this influence warrant further investigation.\u003c/p\u003e \u003cp\u003eThis study focuses on TATB, conducting molecular dynamic (MD) research on its thermal decomposition process. The decomposition products and formation processes at different heating rates are analyzed, aiming to elucidate the reasons behind the effect of heating rate on thermal decomposition temperature. This study establishes a uniform heating range (300\u0026ndash;3000 K) and evaluates the thermal decomposition process and products of TATB at heating rates of 20, 40, 60, and 80 K/ps. It contributes to an enhanced understanding of TATB\u0026rsquo;s thermal decomposition mechanism, providing a reference for its safe usage.\u003c/p\u003e"},{"header":"2. Computational Procedure and Methods","content":"\u003cp\u003eIn this study, the Becke 3-parameter, Lee\u0026ndash;Yang\u0026ndash;Parr method under the density functional theory framework was employed for the structural optimization of TATB molecules and their related molecular groups using the 6-31G(d,p) basis set. Energy calculations were performed with the cc-pVTZ basis set to determine the bond dissociation energies (BDEs) of C-NO\u003csub\u003e2\u003c/sub\u003e, C-NH\u003csub\u003e2\u003c/sub\u003e, N-H, and N-O within the molecule.\u003c/p\u003e \u003cp\u003eA 4\u0026times;4\u0026times;4 TATB supercell model (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) was constructed using the TATB unit cell (CCDC: 1266837). The unit cell parameters of TATB were as follows: a\u0026thinsp;=\u0026thinsp;9.01 \u0026Aring;, b\u0026thinsp;=\u0026thinsp;9.028 \u0026Aring;, c\u0026thinsp;=\u0026thinsp;6.812 \u0026Aring;, α\u0026thinsp;=\u0026thinsp;108.58\u0026deg;, β\u0026thinsp;=\u0026thinsp;91.82\u0026deg;, γ\u0026thinsp;=\u0026thinsp;119.97\u0026deg;, and space group Pī. Each unit cell contained two TATB molecules [19], and the constructed supercell model consisted of 128 TATB molecules. Given that periodic boundary conditions were applied during the simulation, the TATB model could expand periodically in three dimensions, effectively representing a bulk-scale TATB crystal.\u003c/p\u003e \u003cp\u003eMD simulations were conducted on the TATB supercell model using the ReaxFF-lg reactive force field. Numerous studies have previously validated the successful application of the ReaxFF-lg force field in simulating the performance of TATB under shock loading conditions [12], so its suitability was not reverified here. For investigating the relationship between the degree of thermal decomposition of TATB and heating rate, heating simulations were performed on the model at rates of 20, 40, 60, and 80 K/ps. First, energy minimization was performed on the constructed model, followed by 5 ps of isothermal\u0026ndash;isobaric (NPT) relaxation at 300 K. Subsequently, canonical ensemble (NVT) dynamics were employed to heat the model continuously from 300 K to 3000 K at heating rates of 20, 40, 60, and 80 K/ps. The time step was set to 0.1 fs, and dynamic trajectories were recorded every 1000 steps. In MD simulations of the thermal decomposition of EMs, heating rates ranging from 0 K/ps to 100 K/ps are commonly used. Although these rates are significantly higher than the 10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e\u0026ndash;10 K/ps rates used in experiments, numerous theoretical studies have demonstrated that such differences in heating rates do not affect the investigation of chemical reaction mechanisms during decomposition [20].\u003c/p\u003e \u003cp\u003eIn this study, the Gaussian09 software [21] was used to calculate the BDEs of TATB molecules, while the MD simulation was performed using the LAMMPS package [22]. Visualization and postprocessing were conducted using the OVITO software [23], and a custom script was developed to analyze the reaction products and frequencies.\u003c/p\u003e"},{"header":"3. Results and Analysis","content":"\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Structural Analysis of TATB Molecules\u003c/h2\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eBDEs of C-NO\u003csub\u003e2\u003c/sub\u003e, C-NH\u003csub\u003e2\u003c/sub\u003e, N-H, and N-O in TATB molecules\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"2\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBond Type\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eBDE (KJ/mol)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eC-NO\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e293.18\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eC-NH\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e462.92\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eN-H\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e480.27\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eN-O\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e607.07\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eTable\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e presents the BDEs of C-NO\u003csub\u003e2\u003c/sub\u003e, C-NH\u003csub\u003e2\u003c/sub\u003e, N-H, and N-O in TATB molecules after optimization. The BDE of C-NO\u003csub\u003e2\u003c/sub\u003e is much lower than those of C-NH\u003csub\u003e2\u003c/sub\u003e, N-H, and N-O. These BDE values indicate that the C-NO\u003csub\u003e2\u003c/sub\u003e bond is more likely to break in a single molecule.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e3.2 MD Study of TATB Thermal Decomposition\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e illustrates the variation in the number of TATB molecules with temperature at different heating rates. At all four heating rates, no significant decomposition of TATB occurs before the temperature reaches 1000 K. In the 300\u0026ndash;3000 K temperature range, the decomposition rate of TATB decreases as the heating rate increases. When the heating rate is 20 K/ps, the decomposition rate of TATB is more pronounced, while the differences between 60 and 80 K/ps are not significant.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eDSC test values and MD simulation values of TATB at different heating rates\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"4\" nameend=\"c3\" namest=\"c1\"\u003e \u003cp\u003eMD Simulation Values\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c4\"\u003e \u003cp\u003eExperimental Values\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eHeating Rate (K/ps)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eInitial Decomposition Temperature K (T\u003csub\u003eical\u003c/sub\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eHeating Rate\u003c/p\u003e \u003cp\u003e(K*min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eInitial Decomposition Temperature (T\u003csub\u003ei\u003c/sub\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003ePeak Temperature (T\u003csub\u003ep\u003c/sub\u003e)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1200\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e642.43 K\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e644.83 K\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1700\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e654.84 K\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e656.38 K\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1800\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003e15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e661.51 K\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e663.83 K\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1900\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e666.05 K\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e669.01 K\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eThe simulation results show that when the temperature reaches 3000 K, TATB does not fully decompose into stable products such as H\u003csub\u003e2\u003c/sub\u003eO, CO\u003csub\u003e2\u003c/sub\u003e, and N\u003csub\u003e2\u003c/sub\u003e; instead, a large number of clusters are formed. Therefore, the simulation cannot determine a peak temperature (T\u003csub\u003epcal\u003c/sub\u003e) under 3000 K. Nevertheless, the simulation results indicate that the initial decomposition temperature (T\u003csub\u003eical\u003c/sub\u003e) increases with rising heating rates, as shown in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The differential scanning calorimetry (DSC) experimental results of TATB at different heating rates [24] also show that the initial decomposition temperature (T\u003csub\u003ei\u003c/sub\u003e) and peak temperature (T\u003csub\u003ep\u003c/sub\u003e) increase with higher heating rates, which is consistent with the theoretical trends.\u003c/p\u003e \u003cp\u003eThe studies on TATB decomposition under high pressure have shown that pressure increases TATB\u0026rsquo;s stability, hindering its thermal decomposition; the higher the pressure, the more significant this effect [14]. In this simulation, the volume of the TATB model remains constant, and as the temperature increases, internal pressure builds up. The higher the heating rate is, the faster the internal pressure rises, leading to increases in T\u003csub\u003eical\u003c/sub\u003e and T\u003csub\u003ezcal\u003c/sub\u003e. The simulation results of this study support the findings from high-pressure TATB decomposition studies and align with experimental observations.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eBecause the final temperature was set to 3000 K for all simulations, the duration of the simulations differed depending on the heating rate. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e illustrates the time-dependent variation in the quantities of the primary free radicals generated during the thermal decomposition of TATB. At all four heating rates, the radicals\u0026thinsp;\u0026minus;\u0026thinsp;H and \u0026minus;\u0026thinsp;O are the first to appear, whereas \u0026minus;\u0026thinsp;HO and \u0026minus;\u0026thinsp;NO\u003csub\u003e2\u003c/sub\u003e emerge later. This finding suggests that the detachment of hydrogen atoms from the \u0026minus;\u0026thinsp;NH\u003csub\u003e2\u003c/sub\u003e groups is likely the first step in the decomposition of TATB molecules, followed by the detachment of oxygen atoms from the \u0026minus;\u0026thinsp;NO\u003csub\u003e2\u003c/sub\u003e groups.\u003c/p\u003e \u003cp\u003eAccording to the BDE data of static TATB molecules (Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e), \u0026minus;NO\u003csub\u003e2\u003c/sub\u003e is the easiest bond to break. However, in the crystal model, \u0026minus;H breaks first, indicating a discrepancy between the molecular and crystal models. This difference arises because intermolecular interactions and packing arrangements in the crystal structure influence the bonding behavior of TATB molecules and, consequently, affect the bond dissociation process.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e shows the inferred initial decomposition reactions of TATB crystals based on the time-dependent changes in the quantities of decomposition products during heating. Reactions \u003cb\u003eII\u003c/b\u003e and \u003cb\u003eIII\u003c/b\u003e appear early in the decomposition process and result in substantial decomposition. Both reactions, along with subsequent reactions, generate\u0026thinsp;\u0026minus;\u0026thinsp;H and \u0026minus;\u0026thinsp;O, which later combine to form\u0026thinsp;\u0026minus;\u0026thinsp;HO. Reaction \u003cb\u003eI\u003c/b\u003e, which involves intramolecular hydrogen transfer, also produces\u0026thinsp;\u0026minus;\u0026thinsp;HO. During the early stages of heating, the energy supplied to the TATB crystal from external sources is insufficient to drive Reactions \u003cb\u003eII\u003c/b\u003e and \u003cb\u003eIII\u003c/b\u003e extensively because these reactions require more energy. By contrast, Reaction \u003cb\u003eI\u003c/b\u003e requires less energy and is easier to initiate. Therefore, Reaction I is likely to occur earlier than Reactions \u003cb\u003eII\u003c/b\u003e and \u003cb\u003eIII\u003c/b\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e shows the temperature-dependent variations in the quantities of the same free radicals at different heating rates. For the primary ions produced during decomposition, such as \u0026minus;\u0026thinsp;H, \u0026minus;O, \u0026minus;HO, \u0026minus;NO\u003csub\u003e2\u003c/sub\u003e, and \u0026minus;\u0026thinsp;NO, the trends in quantity changes are consistent across different heating rates. As the heating rate increases, the temperature at which these free radicals first appear also rises. This behavior of the primary free radical products aligns with the relationship between heating rate and decomposition rate, in which higher heating rates result in slower TATB decomposition.\u003c/p\u003e \u003cp\u003eBased on Figs.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e and \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e, as \u0026minus;\u0026thinsp;H appears, the structure C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e7\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eN\u003csub\u003e6\u003c/sub\u003e forms after a prolonged heating period, indicating that intermolecular hydrogen transfer occurs during TATB decomposition. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e highlights the peak temperatures corresponding to the maximum quantities of C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e7\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eN\u003csub\u003e6\u003c/sub\u003e structures at different heating rates: 1840 K (20 K/ps), 1980 K (40 K/ps), 2020 K (60 K/ps), and 2380 K (80 K/ps). They are situated between the initial decomposition temperature T\u003csub\u003eical\u003c/sub\u003e and the temperature at which the TATB molecule count reaches zero T\u003csub\u003ezcal\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, the quantity of \u0026minus;\u0026thinsp;HO increases steadily in the later stages of heating at all four heating rates, but it does not exceed the quantities formed in the early stages. The trends in C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e7\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eN\u003csub\u003e6\u003c/sub\u003e structure formation in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e, along with the reaction pathways illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e, indicate that \u0026minus;\u0026thinsp;HO formation in the thermal decomposition process of TATB originates from two possible pathways. In the early stages, \u0026minus;HO is produced through intramolecular hydrogen transfer and the detachment of H and O atoms from \u0026minus;\u0026thinsp;NH\u003csub\u003e2\u003c/sub\u003e and \u0026minus;\u0026thinsp;NO\u003csub\u003e2\u003c/sub\u003e groups on the TATB molecule. In the later stages, \u0026minus;HO is formed through intermolecular hydrogen transfer and subsequent detachment.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThis section analyzes the three primary stable products (H₂O, CO₂, and N₂) generated during the thermal decomposition of TATB. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e presents the time-dependent variations in the quantities of these stable products. At all four heating rates, H₂O is the first stable product to form. Overall, as temperature increases, the quantities of H₂O, CO₂, and N₂ also increase across different heating rates.\u003c/p\u003e \u003cp\u003eIn Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea, at a heating rate of 20 K/ps, the quantity of H₂O tends to stabilize at around 2600 K. In Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb, at a heating rate of 40 K/ps, the quantity of H₂O stabilizes at around 3000 K; at heating rates of 60 and 80 K/ps, the quantity of H₂O continues to increase. Similar trends are observed for N₂ in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea, in which the quantity of N₂ tends to stabilize at around 2800 K at a heating rate of 20 K/ps. For the 40 K/ps heating rate, N₂ stabilizes at 3000 K. By contrast, the quantity of N₂ continues to increase at heating rates of 60 and 80 K/ps.\u003c/p\u003e \u003cp\u003eAs for CO₂, it forms after the breakdown of the six-membered carbon ring, which occurs later in the thermal decomposition process of TATB. Therefore, as noted earlier, with a maximum temperature setting of 3000 K, the higher the heating rate, the slower the decomposition rate, and the shorter the duration of the heating process. This condition reduces the time available for free radicals to collide and react, thereby limiting the formation of CO₂. Consequently, the quantity of CO₂ only increases during the later stages of thermal decomposition. This analysis suggests that at 3000 K, the decomposition of TATB within the model is incomplete.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e compares the temperature-dependent variations in the quantities of the same decomposition products at different heating rates. Because of the pressure within the system inhibiting the decomposition process, higher heating rates result in slower decomposition. Consequently, at the same temperature, the quantities of H₂O, N₂, and CO₂ decrease as the heating rate increases. When the heating rate is faster, free radicals in the model do not have enough time to collide and form stable products, leading to fewer decomposition products.\u003c/p\u003e \u003cp\u003eWithin the 300\u0026ndash;3000 K temperature range, N₂ is the second most abundant final product after H₂O. The formation of N₂ is dependent on the generation of \u0026minus;\u0026thinsp;NH and \u0026minus;\u0026thinsp;NO radicals. Therefore, at higher heating rates, the increased pressure in the simulation system suppresses the formation of \u0026minus;\u0026thinsp;NH and \u0026minus;\u0026thinsp;NO, reducing the quantity of N₂ and delaying its appearance (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). At a heating rate of 20 K/ps, however, the final quantity of N₂ surpasses that of H₂O (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea), which is consistent with the literature [14], that is, the generation of N₂ is accompanied with a reduction in H₂O during TATB thermal decomposition.\u003c/p\u003e \u003cp\u003eIn theoretical simulations, a heating rate of 20 K/ps allows enough time for the free radicals generated during TATB decomposition to fully react, thereby balancing the decomposition rate with the product formation rate. When higher heating rates (40, 60, and 80 K/ps) are used, a higher cutoff temperature is needed to extend the reaction time, allowing sufficient time for free radicals to fully react. Based on the simulation results in this study, when conducting simulations of EMs\u0026rsquo; thermal decomposition, lower heating rates should be used to observe complete reactions if the temperature is set lower, while higher heating rates require a corresponding increase in the cutoff temperature.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAccording to the maximum heat release principle, during a DSC test, the maximum exothermic point for EMs is reached when the quantities of H₂O and CO₂ reach their peaks, corresponding to the thermal decomposition peak temperature T\u003csub\u003ep\u003c/sub\u003e. However, in this simulation, because the cutoff temperature is set to 3000 K, the decomposition process of TATB is not fully completed, preventing the determination of the simulated peak temperature T\u003csub\u003epcal\u003c/sub\u003e. As the heating rate increases, the quantities of H₂O, CO₂, and N₂ decrease (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e), which contradicts the maximum heat release principle. This discrepancy is due to the limitation imposed by the temperature range set in this study. For calculating the variation in T\u003csub\u003epcal\u003c/sub\u003e with heating rate, the final temperature should be increased in the simulation.\u003c/p\u003e \u003cp\u003eThe temperature at which the number of TATB molecules reaches zero T\u003csub\u003ezcal\u003c/sub\u003e shows an upward trend with increasing heating rates, which also does not align with the maximum heat release principle. The reason is that the TATB model used in this study is a crystal model. Moreover, when the NVT ensemble is employed, the entire model remains in an overpressure state once heating begins. As a result, it is difficult for H₂O, CO₂, and N₂ to exist in gaseous form, making the quantities of these decomposition products inaccurate indicators of T\u003csub\u003ezcal\u003c/sub\u003e variations across different heating rates.\u003c/p\u003e \u003cp\u003eTo address this issue, this study tracks the total quantity of internal compounds and fragments in the model as a function of temperature, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e. Under the same temperature conditions, the higher the heating rate, the fewer internal compounds and fragments form within the 300\u0026ndash;3000 K range. This trend is consistent with the variation in the quantities of H₂O, CO₂, and N₂.\u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eWithin the same temperature range (300\u0026ndash;3000 K), the heating rate does not affect the thermal decomposition mechanism of TATB. According to the analysis in this study, the formation of \u0026minus;\u0026thinsp;HO during TATB decomposition occurs via three pathways: (1) intramolecular hydrogen transfer followed by the detachment of \u0026minus;\u0026thinsp;HO in the early stages of the reaction, (2) the detachment of H and O from \u0026minus;\u0026thinsp;NH₂ and \u0026minus;\u0026thinsp;NO₂ groups in TATB to form\u0026thinsp;\u0026minus;\u0026thinsp;HO, and (3) intermolecular hydrogen transfer leading to the release of \u0026minus;\u0026thinsp;HO in the later stages of decomposition.\u003c/p\u003e \u003cp\u003eIn the studied temperature range, the decomposition rate of TATB decreases as the heating rate increases because of the pressure within the simulation system. The initial decomposition temperature of TATB rises with higher heating rates. The heating rate also influences the quantity of decomposition products, particularly those formed in the later stages. The simulation results demonstrate that at lower heating rates, the decomposition process takes longer, allowing more time for collisions between decomposition products and increasing the probability of their combination. As a result, more stable products, such as H₂O, CO₂, and N₂, are formed. Conversely, at higher heating rates, fewer H₂O, CO₂, and N₂ molecules are produced.\u003c/p\u003e "},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eDeclaration of competing interest\u003c/h2\u003e \u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eXianfeng Wei: Wrote the main manuscript, Investigation, review \u0026amp; editing, Supervision, Methodology, Funding acquisition.Shan Sha: Investigation, Data curation. Qingying Duan: Investigation, Data curation.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThe authors gratefully acknowledge the support of NSFC (22173086).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eSlape R J (1984) IHE material qualifcation tests description and criteria, 1984.\u003c/li\u003e\n\u003cli\u003eXu H, Duan X, Li H, Pei C (2015) A novel high-energetic and good-sensitive cocrystal composed of CL-20 and TATB by a rapid solvent/non-solvent method. RSC Adv. 5:95764.\u003c/li\u003e\n\u003cli\u003eHou C, Liu Z, Zhang Y, Chen Y, Zhang S (2017). Study on preparation and properties of TATB/HMX cocrystal explosive. Chinese Journal of Explosive \u0026amp; Propellants. 40(4):6.\u003c/li\u003e\n\u003cli\u003eWang Y, Wang B, Ye Z, Shang Y, Qing H, Li Y (2011) Synthesis of TATB by VNS method. Chin. J. Energ. Mater. 19(2):142-146.\u003c/li\u003e\n\u003cli\u003eZhang C, Jiao F, Li H (2018), Crystal Engineering for Creating Low Sensitivity and Highly Energetic Materials, Cryst. Growth Des. 18:5713-5726.\u003c/li\u003e\n\u003cli\u003eHuang B, Cao M, Wu X, Nie F, Huang H, Hu C (2011) Twinned TATB nanobelts: synthesis, characterization, and formation mechanism. CrystEngComm. 13: 6658-6664.\u003c/li\u003e\n\u003cli\u003eXiong X, He X, Xiong Y, Xue X, Yang H, Zhang C (2020) Correlation between the self-sustaining ignition ability and the impact sensitivity of energetic materials, Energ. Mater. Front. 1:40-49.\u003c/li\u003e\n\u003cli\u003eZuo C, Zhang C (2024) 1,3,5-Triamino-2,4,6-Trinitrobenzene (TATB): Enlightening the way to create new Low-Sensitivity and High-Energy materials from a viewpoint of multiscale. Chem. Eng. J. 490:151737.\u003c/li\u003e\n\u003cli\u003eMa Y, Zhang A, Zhang C, Jiang D, Zhu Y, Zhang C (2014) Crystal packing of low-sensitivity and high-energy explosives. Cryst. Growth Des. 14(9):4703-4713. \u003c/li\u003e\n\u003cli\u003eZhong K, Bu R, Jiao F, Liu G, Zhang C (2022) Toward the defect engineering of energetic materials: A review of the effect of crystal defects on the sensitivity, Chem. Eng. J. 429:132310.\u003c/li\u003e\n\u003cli\u003eWang L, Chen D, Li H, Duan X, Yu Y (2020) Crystal morphology of \u0026beta;-HMX under eight solvents system using molecular dynamics simulation and experiment. Chin. J. Energ. Mater. 28(4):317-329.\u003c/li\u003e\n\u003cli\u003eZhou T, Song H, Huang F (2017) The Slip and Anisotropy of TATB Crystal under Shock Loading via Molecular Dynamics Simulation. Acta Phys. -Chim. Sin. 33(5):949-959.\u003c/li\u003e\n\u003cli\u003eRoman T, Onise S, Maija K (2016) Molecular theory of detonation initiation: Insight from first principles modeling of the decomposition mechanisms of organic nitro energetic materials. Molecules. 21(2):236.\u003c/li\u003e\n\u003cli\u003eSun X, Liang W, Li X, Gao C, Dai R, Wang Z, Zhang Z (2022) Advances of high-temperature and high-pressure physical properties and experimental technology on high-energy insensitive explosive TATB. Chin. J. of High-Pressure Phys. 36(3):030101.\u003c/li\u003e\n\u003cli\u003eDing Y, Wu Y, Wang H, Liu G, Ji W (2014) Effects of TNT on the thermal decomposition performance of RDX. Exp. Mater. 43(05):21-25.\u003c/li\u003e\n\u003cli\u003eLiu J, Zhao N, Zhao F, Song J, Ma H (2015) Preparation of sea urchin-shaped nano-MnO\u003csub\u003e2 \u003c/sub\u003eand its effect on thermal decomposition performance of CL-20. Chin. J. Explos. Propell. 02:27-32+42.\u003c/li\u003e\n\u003cli\u003eZhang T, Guo Y, Li Y, Guo Z, Ma H (2019) Effect of nitrogen-doped graphene oxide on thermal decomposition of HMX. Chin. J. Explos. Propell. 42(04):346-351.\u003c/li\u003e\n\u003cli\u003eCao X, Luo S, Xu L, Meng R (2016) Thermal decomposition of TATB and its thermal explosion characteristics in [Emim] Ac/DMSO solvent. Chin. J. Explos. Propell. 039(001):52-55.\u003c/li\u003e\n\u003cli\u003eHoward H C and Allen C L (1965) The crystal structure of 1,3,5-triamino-2,4,6-trinitrobenzene. Acta Crystallographica, 18: 485.\u003c/li\u003e\n\u003cli\u003eDeng C, Xue X, Chi Y, Li H, Long X, Zhang C (2017) Nature of the enhanced self-heating ability of imperfect energetic crystals relative to perfect ones. J. Phys. Chem. C. 121:12101\u0026minus;12109.\u003c/li\u003e\n\u003cli\u003eFrisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Scalmani G, Barone V, Mennucci B, Petersson G A (2010) Gaussian 09, Revision B.01. Gaussian Inc., Wallingford.\u003c/li\u003e\n\u003cli\u003ePlimpton S (1995) Fast Parallel Algorithms for Short-Range Molecular Dynamics, J. Comput. Phys. 117(1):1-19.\u003c/li\u003e\n\u003cli\u003eStukowski A (2010) Visualization and analysis of atomistic simulation data with OVITO-the Open Visualization Tool, Modelling Simul. Mater. Sci. Eng. 18:015012.\u003c/li\u003e\n\u003cli\u003eLi P, Aodeng G, Li C, Duan X, Pei C (2019) Construction and thermal decomposition kinetics of the keel-like nanostructure TATB. Chin. J. Energ. Mater. 27(02):137-143.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"journal-of-molecular-modeling","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jmmo","sideBox":"Learn more about [Journal of Molecular Modeling](https://www.springer.com/journal/894)","snPcode":"894","submissionUrl":"https://submission.nature.com/new-submission/894/3","title":"Journal of Molecular Modeling","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Energetic material, Thermal decomposition, Reactive molecular dynamics, Decomposition products","lastPublishedDoi":"10.21203/rs.3.rs-5457870/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5457870/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eTo clarify the effect of heating rate on the thermal decomposition process of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), this study employs molecular dynamic simulations to investigate the thermal decomposition of TATB at heating rates of 20, 40, 60, and 80 K/ps. The initial temperature is uniformly set to 300 K, while the final temperature is set to 3000 K. Results indicate that within the temperature range of 300–3000 K, the thermal decomposition rate of TATB decreases with increasing heating rate, whereas the initial decomposition temperature of TATB increases, consistent with the experimental pattern. Within the studied temperature range, a lower heating rate results in a longer decomposition time, leading to increased collision reaction time of decomposition products, a higher probability of formation, and more stable products, such as H\u003csub\u003e2\u003c/sub\u003eO, CO\u003csub\u003e2\u003c/sub\u003e, and N\u003csub\u003e2\u003c/sub\u003e. Conversely, at higher heating rates, the quantities of H\u003csub\u003e2\u003c/sub\u003eO, CO\u003csub\u003e2\u003c/sub\u003e, and N\u003csub\u003e2\u003c/sub\u003e are reduced.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eMethods：\u003c/strong\u003eThe Gaussian09 software was used to calculate the BDEs of TATB molecules, while the MD simulation was performed using the LAMMPS package. Visualization and postprocessing were conducted using the OVITO software, and a custom script was developed to analyze the reaction products and frequencies.\u003c/p\u003e","manuscriptTitle":"Molecular Dynamic Simulation Study on the Influence of Heating Rate on the Thermal Decomposition Process of 1,3,5-Triamino- 2,4,6-Trinitrobenzene (TATB)","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-12-03 10:34:42","doi":"10.21203/rs.3.rs-5457870/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-11-28T10:38:19+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-11-28T06:41:14+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"3763343639799710880860670754871035815","date":"2024-11-25T02:38:11+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-11-21T08:00:27+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"295080408802732342243849789866960272200","date":"2024-11-21T00:24:56+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"57021515750958323111214893058743118558","date":"2024-11-20T18:41:06+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-11-20T16:28:49+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-11-20T15:18:46+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-11-20T15:17:15+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Molecular Modeling","date":"2024-11-15T05:44:22+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-molecular-modeling","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jmmo","sideBox":"Learn more about [Journal of Molecular Modeling](https://www.springer.com/journal/894)","snPcode":"894","submissionUrl":"https://submission.nature.com/new-submission/894/3","title":"Journal of Molecular Modeling","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"e4a2bbbb-a79a-4e32-8afc-664147a60077","owner":[],"postedDate":"December 3rd, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-01-20T16:06:23+00:00","versionOfRecord":{"articleIdentity":"rs-5457870","link":"https://doi.org/10.1007/s00894-024-06270-y","journal":{"identity":"journal-of-molecular-modeling","isVorOnly":false,"title":"Journal of Molecular Modeling"},"publishedOn":"2025-01-14 15:57:36","publishedOnDateReadable":"January 14th, 2025"},"versionCreatedAt":"2024-12-03 10:34:42","video":"","vorDoi":"10.1007/s00894-024-06270-y","vorDoiUrl":"https://doi.org/10.1007/s00894-024-06270-y","workflowStages":[]},"version":"v1","identity":"rs-5457870","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5457870","identity":"rs-5457870","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}