Chemical Physics最新文献_第7页

N-(4-(1,3-benzothiazol-2-ylcarbamoyl)phenyl)isonicotinamide as corrosion mitigator for mild steel in 1 M HCl: A multifaceted study integrating synthesis, characterization, and molecular modelling N-(4-(1,3-苯并噻唑-2-基氨基甲酰基)苯基)异烟酰胺作为低碳钢在 1 M HCl 中的缓蚀剂：集合成、表征和分子建模于一体的多方面研究

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-09-29 DOI: 10.1016/j.chemphys.2024.112471

Gopal Senthilkumar , Savarinathan Maria Rayappan , Arumugam Ramachandran , Solaiyappan Ayyappan , Pitchai Marimuthu

Newly synthesized, cost-effective corrosion inhibitor, N-(4-(1,3-benzothiazol-2-ylcarbamoyl)phenyl)isonicotinamide (BIA) was evaluated for mild steel/1M HCl interface. BIA showed a maximum inhibition efficiency of 90.40 % at 100 ppm and 303 ± 1 K, with efficiency increasing with concentration but decreasing with temperature. Inhibitor’s adsorption followed Langmuir isotherm via physicochemical interactions. Activation parameters revealed BIA retards both metal dissolution and hydrogen evolution held in unimolecular process. Potentiodynamic polarization (PDP) divulged BIA as a mixed-type, impeding charge-transfer. Electrochemical impedance spectra (EIS) confirmed BIA forms a protective double layer, blocking active sites at the interface. Surface analysis supported a protective film formation. Global and local reactivity descriptors using DFT/B3LYP/6-311G++(d,p) were calculated to relate inhibition efficiency with BIA’s electronic properties. Molecular dynamics simulation (MDS) showed an interaction energy of −224.7 kJ/mol between BIA and Fe(1 1 0) at 303 K, with Radial Distribution Function (RDF) showing bond lengths under 3.5 Å, confirming a chemical interaction. Theoretical results align with experimental data.

对新合成的经济型缓蚀剂 N-(4-(1,3-苯并噻唑-2-基氨基甲酰基)苯基)异烟酰胺（BIA）进行了评估，用于低碳钢/1M HCl 界面。在 100 ppm 和 303 ± 1 K 条件下，BIA 的最大抑制效率为 90.40%，效率随浓度的增加而增加，但随温度的升高而降低。通过物理化学作用，抑制剂的吸附遵循 Langmuir 等温线。活化参数显示，BIA 在单分子过程中可阻止金属溶解和氢演化。电位极化（PDP）表明，BIA 是一种混合型吸附剂，阻碍电荷转移。电化学阻抗谱（EIS）证实 BIA 形成了双层保护膜，阻挡了界面上的活性位点。表面分析支持保护膜的形成。利用 DFT/B3LYP/6-311G++(d,p) 计算了全局和局部反应性描述符，从而将抑制效率与 BIA 的电子特性联系起来。分子动力学模拟 (MDS) 显示，在 303 K 时，BIA 与 Fe(1 1 0) 之间的相互作用能为 -224.7 kJ/mol，径向分布函数 (RDF) 显示键长小于 3.5 Å，证实了化学作用。理论结果与实验数据一致。

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引用次数: 0

Nernst slope and the constant surface charge density behind the ion adsorption-origin membrane potential 离子吸附源膜电位背后的 Nernst 斜坡和恒定表面电荷密度

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-09-27 DOI: 10.1016/j.chemphys.2024.112462

H. Tamagawa , D.L. Anh , M. Sasaki , W. Lin , B. Delalande

Although continuous mobile ion passage across the plasma membrane is responsible for the generation of the membrane potential, some experiments suggest that the membrane potential can be generated even without the ion passage across the membrane. This potential could be due to the ion adsorption–desorption phenomenon, and it is even possible to derive a potential formula under such a mechanism. This potential formula is somehow identical to the well-known Nernst equation. We investigated this potential formula in depth and found that the profile of “the membrane surface potential versus the logarithm of ion concentration” exhibits the Nernst slope, and this Nernst slope is the key to the identical potential formula to the Nernst equation even for the system without the passage of ions across the membrane. This work may trigger new information about the membrane potential generation mechanism.

虽然连续流动的离子穿过质膜是膜电位产生的原因，但一些实验表明，即使没有离子穿过膜，膜电位也能产生。这种膜电位可能是由于离子的吸附-解吸现象产生的，在这种机制下甚至可以推导出一个膜电位公式。这个电势公式在某种程度上与著名的内斯特方程相同。我们对这个电势公式进行了深入研究，发现 "膜表面电势与离子浓度对数 "的曲线呈现奈氏斜率，而这个奈氏斜率正是即使在没有离子穿过膜的系统中，电势公式也与奈氏方程相同的关键所在。这项工作可能会引发有关膜电位产生机制的新信息。

引用次数: 0

Facile synthesis of ultrafine WO3 nanoparticles for highly sensitive acetoin biomarker gas detection 用于高灵敏乙炔素生物标记气体检测的超细 WO3 纳米粒子的简易合成

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-09-26 DOI: 10.1016/j.chemphys.2024.112470

Jiale Kang , Daohan Liu , Wenxiu Ji , Chunxiao Lv , Shiming Liang , Xiumei Ma , Zhengyou Zhu

Facile synthesis of metal oxide semiconductors (MOSs) nanoparticles with ultrafine size is quite promising to improve gas sensing performance due to the large effect of the particle size on the electron depletion layer (EDL), however, which is currently difficult to realize. In this work, we synthesized ultrafine WO₃ nanoparticles of 20 ∼ 30 nm via room-temperature hydrolysis with following annealing and investigated the gas sensing performance of the WO₃ nanoparticles towards acetoin biomarker released by Listeria monocytogenes (LMs). The WO₃ gas sensor displays high response (R_a/R_g = 32.0@5 ppm), excellent selectivity and low detection limit at 140 °C. The ultrafine size of WO₃ comparable to its Debye length can lead to a larger variation of EDL thus a higher sensor response. Our work has provided a facile, low cost and large-scale synthetic route to constructing high-performance acetoin biomarker gas sensors and might contribute to the development for LMs detection.

由于粒径对电子耗尽层（EDL）的影响很大，因此方便地合成超细尺寸的金属氧化物半导体（MOS）纳米粒子在提高气体传感性能方面大有可为。在这项工作中，我们通过室温水解和退火合成了 20 ∼ 30 nm 的超细 WO3 纳米粒子，并研究了 WO3 纳米粒子对单核细胞增生李斯特菌（LMs）释放的乙酰丙酮生物标记物的气体传感性能。WO3 气体传感器在 140 °C时显示出高响应（Ra/Rg = 32.0@5 ppm）、优异的选择性和低检测限。WO3 的超细尺寸与其 Debye 长度相当，可导致 EDL 的较大变化，从而提高传感器的响应。我们的工作为构建高性能乙炔类生物标记气体传感器提供了一条简便、低成本和大规模的合成途径，并可能为 LMs 检测的开发做出贡献。

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引用次数: 0

First-principles calculations to investigate optoelectronic of transition-metal half-Heusler alloys MTiSn (M = Pd and Pt) for optoelectronics applications 通过第一性原理计算研究过渡金属半赫斯勒合金 MTiSn（M = Pd 和 Pt）在光电子学中的应用

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-09-25 DOI: 10.1016/j.chemphys.2024.112469

M. Musa Saad H.-E. , B.O. Alsobhi

The structural, mechanical, optical, and electronic properties of half-Heuslers MTiSn (M = Pd and Pt) are investigated using FP-LAPW incorporating the GGA-PBE. MTiSn crystallize in ferromagnetic (FM) and cubic structure (F-43m; C1_b) with lattice constants of 6.216 Å and 6.241 Å, respectively, in good agreement with the available data. Elastic constants

C_{ij}

reveal that MTiSn meet the mechanical stability criteria with notable thermodynamic properties. Also, we have conducted a detailed analysis of optical properties, encompassing the dielectric function, absorption coefficient, optical conductivity, optical refractivity, and extinction coefficient. It is found that PtTiSn shows higher optical responses than PdTiSn at low and high energy ranges. In terms of electronic properties, MTiSn demonstrate narrow bandgap semiconductor characteristics with an indirect bandgap of

E_{g}

= 0.507 eV (M = Pd) and

E_{g}

= 0.782 eV (M = Pt). The notable optoelectronic responses have also been examined, indicating the high potential of MTiSn materials for optoelectronic applications.

利用结合了 GGA-PBE 的 FP-LAPW 方法研究了半赫勒斯 MTiSn（M = Pd 和 Pt）的结构、机械、光学和电子特性。MTiSn 晶体呈铁磁性（FM）和立方结构（F-43m；C1b），晶格常数分别为 6.216 Å 和 6.241 Å，与现有数据十分吻合。弹性常数 Cij 表明 MTiSn 符合机械稳定性标准，并具有显著的热力学特性。此外，我们还对光学特性进行了详细分析，包括介电函数、吸收系数、光导率、光折射率和消光系数。研究发现，在低能量和高能量范围内，铂钛锰的光学响应均高于钯钛锰。在电子特性方面，MTiSn 显示出窄带隙半导体特性，间接带隙为 Eg = 0.507 eV（M = Pd）和 Eg = 0.782 eV（M = Pt）。此外，还研究了显著的光电响应，这表明 MTiSn 材料在光电应用方面具有巨大潜力。

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引用次数: 0

A study using physical sphere-in-contact models to investigate the structure of close-packed nanoparticles supported on flat hexagonal, square and trigonal lattices 利用物理球接触模型研究平面六边形、方形和三棱晶格上支撑的紧密堆积纳米粒子的结构

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-09-22 DOI: 10.1016/j.chemphys.2024.112464

Constantinos D. Zeinalipour-Yazdi

The tailored design of nanoparticles becomes more important with the advancement of heterogeneous catalysis and materials science. The formation of nanoparticles in catalysts with a specific geometry of the active site becomes necessary to improve activity and selectivity in catalysis. Here we have used physical sphere-in-contact models of various nanoparticles with hexagonal, square and trigonal geometries on flat close-packed surfaces to understand how the distribution of (100) and (111) sites changes as a function of nanoparticle (NP) size in a simplified model of nanoparticle supported metals. The results from this approach clearly show that in 2-layer NPs that have a hexagonal base have 2–3 times more (100) sites than the square and trigonal base NPs as a function of the number of atoms in the NP. In 3D isotropic NPs, this phenomenon is even more pronounced than the 2-layer NPs. We derive equations that estimate the number of (100), (111), the number of atoms and the aspect ratio as a function of n. These equations are important in tailoring the properties of NPs supported on close-packed metal surfaces, which may find applications in materials science, nanotechnology and catalysis.

随着异相催化和材料科学的发展，纳米粒子的定制设计变得越来越重要。为了提高催化活性和选择性，有必要在催化剂中形成具有活性位点特定几何形状的纳米粒子。在此，我们使用物理球接触模型，在平面紧密堆积表面上建立了六角形、方形和三角形几何形状的各种纳米粒子，以了解在纳米粒子支撑金属的简化模型中，(100) 和 (111) 位点的分布如何随纳米粒子（NP）尺寸的变化而变化。这种方法的结果清楚地表明，在具有六角形基底的 2 层 NP 中，与 NP 中的原子数相比，其 (100) 位点的数量是方形和三角形基底 NP 的 2-3 倍。在三维各向同性 NP 中，这种现象比两层 NP 更为明显。我们推导出了估算 (100)、(111)、原子数和长宽比与 n 的函数关系的方程。这些方程对于调整支撑在紧密堆积金属表面上的 NPs 的性质非常重要，这些 NPs 可应用于材料科学、纳米技术和催化等领域。

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引用次数: 0

First-principles investigation of structural, electronic, optical and thermoelectric performance of stable inorganic double perovskites A2AlAgBr6 (A=K, Rb, Cs) for energy harvesting 用于能量收集的稳定无机双包晶石 A2AlAgBr6（A=K、Rb、Cs）的结构、电子、光学和热电性能的第一性原理研究

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-09-21 DOI: 10.1016/j.chemphys.2024.112463

Muhammad Jawad , Amin Ur Rahman , Shafaat Hussain Mirza , Noor ul Amin , Muhammad Faizan , Abdullah Saad Alsubaie , Salah M. El-Bahy

In this work, the structural, electronic, optical and thermoelectric properties of Cs₂AlAgBr₆, K₂AlAgBr₆ and Rb₂AlAgBr₆ have been investigated using WIEN2k code. All the three double perovskites show stability. The stability is confirmed by calculating their formation energy, tolerance factor and molecular dynamic simulations. The electronic properties revealed the understudy compounds as semiconductors of direct band gap of 2.62, 2.61 and 2.59 eV for Cs₂AlAgBr₆, K₂AlAgBr₆ and Rb₂AlAgBr₆, respectively. The absorption band of our compounds is mostly in the ultraviolet energy range which is particularly significant for optoelectronic devices. The studied double perovskites exhibit a large Seebeck coefficient and electrical conductivity, which is significant for the high figure of merit. These properties make them particularly suitable for thermoelectric (TE) devices and other photovoltaic applications, as their high figure of merit at low temperatures opens up new possibilities for these materials.

本研究使用 WIEN2k 代码研究了 Cs2AlAgBr6、K2AlAgBr6 和 Rb2AlAgBr6 的结构、电子、光学和热电特性。所有这三种双包晶都显示出稳定性。通过计算它们的形成能、容忍因子和分子动力学模拟，证实了它们的稳定性。电子特性显示，Cs2AlAgBr6、K2AlAgBr6 和 Rb2AlAgBr6 的直接带隙分别为 2.62、2.61 和 2.59 eV。我们的化合物的吸收带主要在紫外线能量范围内，这对光电设备尤为重要。所研究的双包晶石具有较大的塞贝克系数和电导率，这对高优点非常重要。这些特性使它们特别适用于热电（TE）设备和其他光电应用，因为它们在低温下的高优点为这些材料开辟了新的可能性。

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引用次数: 0

Electrochemical determination of 4-nitrophenol using functionalized graphene oxide/functionalized multi-walled carbon nanotubes hybrid material modified glassy carbon electrode 使用功能化氧化石墨烯/功能化多壁碳纳米管杂化材料修饰的玻璃碳电极电化学测定 4-硝基苯酚

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-09-21 DOI: 10.1016/j.chemphys.2024.112468

Pasar Nizar Saeed, Muhammet Guler

Herein, a novel carboxylated multi-walled carbon nanotubes-carboxylated graphene oxide coated glassy carbon electrode (f-MWCNTs/f-GO/GCE) was prepared for electrochemical determination of 4-nitropehenol (4-NP). The sensor was characterized using fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), raman spectroscopy, and powder x-ray diffraction (XRD). Electrochmical experiments were performed using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and amperometry. The resulting f-MWCNTs/f-GO/GCE could be performed for quick, sensitive, and selective determination of 4-NP in the presence of other electroactive compounds. 4-NP was electrochemically detected depending on the reduction of 4-NP at −0.65 V potential using amperometric method. Under the optimum condutions, the sensor showed excellent response to the determination of 4-NP with three linear detection ranges from 0.018 to 700 µM. The sensor exhibited extremely low limit of detection (5.4 nM). Also, the fabricated sensor was used for detection of 4-NP in different water samples.

本文制备了一种新型羧基多壁碳纳米管-羧基氧化石墨烯涂层玻璃碳电极（f-MWCNTs/f-GO/GCE），用于电化学测定 4-硝基苯酚（4-NP）。使用傅立叶变换红外光谱（FTIR）、场发射扫描电子显微镜（FE-SEM）、拉曼光谱和粉末 X 射线衍射（XRD）对传感器进行了表征。电化学实验采用循环伏安法（CV）、电化学阻抗谱法（EIS）和安培计法进行。所制备的 f-MWCNTs/f-GO/GCE 可用于在存在其他电活性化合物的情况下快速、灵敏、选择性地测定 4-NP。4-NP 的电化学检测取决于 4-NP 在 -0.65 V 电位下的还原，采用的是安培法。在最佳条件下，传感器对 4-NP 的检测显示出极佳的响应，在 0.018 至 700 µM 之间有三个线性检测范围。该传感器的检测限极低（5.4 nM）。此外，该传感器还被用于检测不同水样中的 4-NP 含量。

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引用次数: 0

Theoretical Investigation of the structure and Raman scattering properties of Hoogsteen- and Watson-Crick-type Adenine-Thymine base pair 胡格斯坦和沃森-克里克型腺嘌呤-酪氨酸碱基对的结构和拉曼散射特性的理论研究

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-09-19 DOI: 10.1016/j.chemphys.2024.112465

Yu Xiao , Feng-Yi Zhang , Ming-Jun Ma , Si-Jun Lu , Yong-Jun Zhang , Xiao-Yu Zhao , Ya-Xin Wang , Kun Zhang , Hong-Liang Xu

Hoogsteen (HG) and Watson-Crick (WC) adenine–thymine (A-T) base pairs are fundamental to gene expression and genomic stability. Our research applied density functional theory (DFT) calculations to analyze these base pairs, demonstrating that linking them with ribose or deoxyribose and their immersion in solvents markedly enhances the distinctions in their optical properties. DFT results reveal that N···HN hydrogen bonds in both HG and WC pairs exhibit characteristics of both ionic and covalent bonds, playing a crucial role in their stability. While WC base pairs demonstrate stronger orbital interactions, they also experience greater repulsion than HG pairs. This repulsion offsets the positive interactions to a degree, making the interaction energy of WC pairs slightly lower than that of HG pairs. Furthermore, the distinct conformations of these base pairs result in different vibrational modes, suggesting Raman spectroscopy as an effective method for distinguishing between WC and HG base pairs.

Hoogsteen（HG）和 Watson-Crick （WC）腺嘌呤-胸腺嘧啶（A-T）碱基对是基因表达和基因组稳定性的基础。我们的研究运用密度泛函理论（DFT）计算来分析这些碱基对，结果表明，将它们与核糖或脱氧核糖连接起来并浸入溶剂中，能显著增强它们的光学特性差异。DFT 结果表明，HG 和 WC 碱基对中的 N-HN 氢键同时具有离子键和共价键的特征，对它们的稳定性起着至关重要的作用。虽然 WC 碱基对表现出更强的轨道相互作用，但它们也比 HG 碱基对具有更大的斥力。这种斥力在一定程度上抵消了正相互作用，使得 WC 碱基对的相互作用能略低于 HG 碱基对。此外，这些碱基对的不同构象导致了不同的振动模式，这表明拉曼光谱是区分 WC 和 HG 碱基对的有效方法。

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引用次数: 0

Molecular behavior of 1-acetoxymethyl-3-methylimidazolium tetrafluoroborate and DMSO binary system 1-acetoxymethyl-3-methylimidazolium tetrafluoroborate and DMSO 二元体系的分子行为

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-09-19 DOI: 10.1016/j.chemphys.2024.112467

Shuyan Liu , Yuxin Jiang , Peng Zhao , Xianzhen Xu , Xiaohui Liu , Yu Zhou

Ester-functionalized ionic liquids (ILs) are widely applied in electrochemistry, separation, reduction and extraction, but there are few basic researches on them. This study investigates the hydrogen bonding interactions between the ester-functionalized ILs and dimethyl sulfoxide (DMSO), as well as compares it to the ethyl acetate–DMSO (CH₃COOCH₂CH₃–DMSO) system. Experimental and quantum chemical calculation sections were employed for this purpose. The results demonstrate that: (1) The hydrogen bonding interactions in the 1-acetoxymethyl-3-methylimidazolium tetrafluoroborate (AOMMIMBF₄–DMSO) and 1-acetoxyethyl-3-methylimidazolium tetrafluoroborate (AOEMIMBF₄–DMSO) systems are stronger than that in CH₃COOCH₂CH₃–DMSO system. (2) AOMMIMBF₄–DMSO and AOEMIMBF₄–DMSO systems exhibit comparable interaction strengths. (3) The complexes were identified by the excess spectra and quantum chemical calculations, which are 2AOMMIMBF₄, 2AOMMIMBF₄–DMSO, AOMMIMBF₄–DMSO and [AOMMIM]⁺−DMSO complexes, respectively. This study enhances understanding of hydrogen bonding interactions between ester-functionalized IL and DMSO, and provides a theoretical basis for further applications of ester-functionalized ILs.

酯官能化离子液体（ILs）被广泛应用于电化学、分离、还原和萃取等领域，但相关的基础研究却很少。本研究探讨了酯官能化离子液体与二甲基亚砜（DMSO）之间的氢键相互作用，并将其与乙酸乙酯-DMSO（CH3COOCH2CH3-DMSO）体系进行了比较。为此采用了实验和量子化学计算部分。结果表明(1) 1-acetoxymethyl-3-methylimidazolium tetrafluoroborate (AOMMIMBF4-DMSO) 和 1-acetoxyethyl-3-methylimidazolium tetrafluoroborate (AOEMIMBF4-DMSO) 体系中的氢键相互作用强于 CH3COOCH2CH3-DMSO 体系。(2）AOMMIMBF4-DMSO 和 AOEMIMBF4-DMSO 体系的相互作用强度相当。(3) 通过过量光谱和量子化学计算确定了配合物，它们分别是 2AOMMIMBF4、2AOMMIMBF4-DMSO、AOMMIMBF4-DMSO 和 [AOMMIM]+-DMSO 配合物。这项研究加深了人们对酯官能化 IL 与 DMSO 之间氢键相互作用的理解，为酯官能化 IL 的进一步应用提供了理论依据。

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引用次数: 0

Heat- and shock-induced pyrolysis of crystalline and amorphous TNT revealed by ReaxFF-lg simulations ReaxFF-lg 模拟揭示了结晶和无定形 TNT 的热解和冲击诱导热解过程

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-09-19 DOI: 10.1016/j.chemphys.2024.112466

Shuangfei Zhu , Chaowen Yang , Junjun Zhao , Shuhai Zhang , Ruijun Gou , Yang Liu , Yahong Chen

The decomposition mechanisms of crystalline and amorphous TNT were studied through ReaxFF-lg simulations under the heat-loaded and shock-loaded. Their differences were elucidated from the initial decay reactions, activation energy, products and the clusters. Results showed that the heat-induced pyrolysis of two systems differed slight, but the shock-induced pyrolysis differed large. The decomposition reactions of amorphous and crystalline models are similar, but the nitro oxidation of TNT is only found in amorphous. Dimerization and intermolecular H-transfer were found at the constant temperature and MSST simulations, and intermolecular O-transfer were only found at the constant temperature simulations. For MSST simulation, products in crystalline formed later than in amorphous, and the number of clusters in crystalline is much larger than in amorphous, which indicating crystalline TNT would be induced early through shock wave. These findings could help to increase the understanding for the thermolysis behavior and safety of crystalline and amorphous energetic materials.

通过 ReaxFF-lg 模拟研究了晶体和无定形 TNT 在热负荷和冲击负荷下的分解机理。从初始衰变反应、活化能、产物和团聚体等方面阐明了它们之间的差异。结果表明，两种体系的热诱导热分解差异较小，但冲击诱导热分解差异较大。无定形模型和晶体模型的分解反应相似，但 TNT 的硝基氧化反应只出现在无定形模型中。在恒温模拟和 MSST 模拟中发现了二聚化和分子间 H 转移，而分子间 O 转移只在恒温模拟中发现。在MSST模拟中，晶体中产物的形成晚于非晶体，且晶体中簇的数量远大于非晶体，这表明晶体TNT通过冲击波诱导的时间较早。这些发现有助于加深对晶体和非晶态高能材料热分解行为和安全性的理解。

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引用次数: 0