TATB/氟聚物PBX力学性能、结合能和爆炸性能的模拟计算

Molecular dynamics （MD） method was used to simulate 1,3,5-triamino-2,4,6-trinitrobenzene （TATB） coated with fluorine containing polymers. The mechanical properties and binding energies of PBXs were obtained. It was found that when the number of chain monomers of fluorine containing polymers was the same, the elasticity of TATB/F2314 was increased more greatly than others and the binding energy of TATB/F2311 was the largest among four PBXs. Detonation heat and velocity of such four PBXs were calculated according to theoretical and empirical formulas. The results show that the order of detonation heat is TATB〉TATB/PVDF〉TATB/F2311〉TATB/ F2314 〉 TATB/PCTFE while the order of detonation velocity is TATB/PVDF 〈 TATB/F2311 〈 TATB/F2314 〈 TATB/PCTFE 〈TATB.     

Intermolecular Vibration Energy Transfer Process in Two CL-20-Based Cocrystals Theoretically Revealed by Two-Dimensional Infrared Spectra

Inspired by the recent cocrystallization and theory of energetic materials, we theoretically investigated the intermolecular vibrational energy transfer process and the non-covalent intermolecular interactions between explosive compounds. The intermolecular interactions between 2,4,6-trinitrotoluene (TNT) and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and between 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) and CL-20 were studied using calculated two-dimensional infrared (2D IR) spectra and the independent gradient model based on the Hirshfeld partition (IGMH) method, respectively. Based on the comparison of the theoretical infrared spectra and optimized geometries with experimental results, the theoretical models can effectively reproduce the experimental geometries. By analyzing cross-peaks in the 2D IR spectra of TNT/CL-20, the intermolecular vibrational energy transfer process between TNT and CL-20 was calculated, and the conclusion was made that the vibrational energy transfer process between CL-20 and TNTII (TNTIII) is relatively slower than between CL-20 and TNTI. As the vibration energy transfer is the bridge of the intermolecular interactions, the weak intermolecular interactions were visualized using the IGMH method, and the results demonstrate that the intermolecular non-covalent interactions of TNT/CL-20 include van der Waals (vdW) interactions and hydrogen bonds, while the intermolecular non-covalent interactions of HMX/CL-20 are mainly comprised of vdW interactions. Further, we determined that the intermolecular interaction can stabilize the trigger bond in TNT/CL-20 and HMX/CL-20 based on Mayer bond order density, and stronger intermolecular interactions generally indicate lower impact sensitivity of energetic materials. We believe that the results obtained in this work are important for a better understanding of the cocrystal mechanism and its application in the field of energetic materials.     

HMX晶体和HMX/F2311 PBXs力学性能的MD模拟研究

用分子动力学方法, 在295 K NVT系综和COMPASS力场下, 对环四甲撑四硝胺(HMX)晶体和F₂₃₁₁沿HMX (001), (010)和(100)晶面所构成PBXs模型的力学性能进行模拟研究. 结果表明, 加入F₂₃₁₁降低了HMX的刚性, 增强了它的延展性. 在HMX (100)面上添加F₂₃₁₁对提高体系的延展性较显著. 为考察温度对力学性能的影响及其机理, 在245～445 K范围完成对HMX (100)/F₂₃₁₁ PBX的MD模拟. 力学分析表明, 随温度增加HMX (100)/F₂₃₁₁的延展性呈抛物线变化规律, 归因于F₂₃₁₁分子链的运动及其构象随温度的变化.     

Structure-kinetics relationships of thermodestruction of some framework nitramines

Thermal decomposition of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW, CL-20) and its oxa-analogs containing four and three nitramine fragments, in the gas phase and in solution predominantly follows the first order kinetics, whereas in the solid phase it proceeds with acceleration. Replacement of the two nitramine groups in the five-membered cycles of the molecule CL-20 by oxa groups practically does not affect the rate of decomposition of oxanitroderivatives in the solid phase. Substitution of the nitro group in one of oxa-nitroderivatives by R = H, NO, COCH₃, CH₂N(NO₂)CH₃ differently affects the rate of decomposition. For R = H the rate of decomposition increases; when R = COCH₃, CH₂N(NO₂)CH₃, it decreases; for R = NO, the rate of decomposition remains constant. For the studied compounds the activation parameters of thermal decomposition are determined in the solution, the gas phase, and the solid phase. In general, the reactivity of nitramines depends on the length of the weakest bond N-NO₂, which is affected by the conformation of the nitro group.     

Nickel-mediated N–N bond formation and N2O liberation via nitrogen oxyanion reduction

The syntheses of (DIM)Ni(NO₃)₂ and (DIM)Ni(NO₂)₂, where DIM is a 1,4-diazadiene bidentate donor, are reported to enable testing of bis boryl reduced N-heterocycles for their ability to carry out stepwise deoxygenation of coordinated nitrate and nitrite, forming O(Bpin)₂. Single deoxygenation of (DIM)Ni(NO₂)₂ yields the tetrahedral complex (DIM)Ni(NO)(ONO), with a linear nitrosyl and κ¹-ONO. Further deoxygenation of (DIM)Ni(NO)(ONO) results in the formation of dimeric [(DIM)Ni(NO)]₂, where the dimer is linked through a Ni–Ni bond. The lost reduced nitrogen byproduct is shown to be N₂O, indicating N–N bond formation in the course of the reaction. Isotopic labelling studies establish that the N–N bond of N₂O is formed in a bimetallic Ni₂ intermediate and that the two nitrogen atoms of (DIM)Ni(NO)(ONO) become symmetry equivalent prior to N–N bond formation. The [(DIM)Ni(NO)]₂ dimer is susceptible to oxidation by AgX (X = NO₃⁻, NO₂⁻, and OTf⁻) as well as nitric oxide, the latter of which undergoes nitric oxide disproportionation to yield N₂O and (DIM)Ni(NO)(ONO). We show that the first step in the deoxygenation of (DIM)Ni(NO)(ONO) to liberate N₂O is outer sphere electron transfer, providing insight into the organic reductants employed for deoxygenation. Lastly, we show that at elevated temperatures, deoxygenation is accompanied by loss of DIM to form either pyrazine or bipyridine bridged polymers, with retention of a BpinO⁻ bridging ligand.

Deoxygenation of nitrogen oxyanions coordinated to nickel using reduced borylated heterocycles leads to N–N bond formation and N₂O liberation. The nickel dimer product facilitates NO disproportionation, leading to a synthetic cycle.     

Molecular dynamics simulations of trans-1,4,5,8-tetranitro-1,4,5,8-tetraazadecalin-based polymer-bonded explosives

Molecular dynamics has been applied to investigate the low-sensitivity explosive TNAD (trans-1,4,5,8-tetranitro-1,4,5,8-tetraazadecalin)-based polymer-bonded explosives (PBXs) with four typical fluorine polymers, PVDF (polyvinylidenedifluoride), PCTFE (polychlorotrifluoroethylene), F(2311) (fluorine rubber), and F(2314) (fluorine resin). The elastic constants, mechanical properties (tensile modulus, bulk modulus, shear modulus, and Poission ratio), binding energies, and detonation performances are first reported for the TNAD-based PBXs. The results show that the mechanical properties of TNAD can be effectively improved by the addition of small amounts of fluorine polymers, and the overall effect of fluorine polymers on the mechanical properties of the PBXs along three crystalline surfaces is (001) > (010) > (100). On each crystal surface, improvement in the ductibility made by the fluorine polymers changes approximately in the sequence of PVDF > F(2311) > F(2314) > PCTFE. The binding energies between different TNAD crystalline surfaces and different polymer binders with the same chain segment or mass fraction both decrease in the order of (010) > (100) > (001). The binding properties of the polymers with the same chain segment on each crystal surface of TNAD increase as PVDF < F(2311) < F(2314) < PCTFE, while those of different polymers in the same content decrease in the sequence of PVDF > F(2311) > F(2314) > PCTFE. The detonation performances of the PBXs decrease in comparison with the pure crystal, but they are superior to those of TNT.     

Structure of a bimolecular crystal of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane and methoxy-<Emphasis Type="Italic">NNO</Emphasis>-azoxymethane

The crystal structure of the bimolecular crystal of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and methoxy-NNO-azoxymethane (МАМ) (1:2) is studied. The CL-20 molecules adopt a ζ-conformation. The crystal structure is formed by layers of CL-20 and МАМ molecules, between which there are shortened NO^δ–?N^δ+O contacts of the neighboring CL-20 and МАМ molecules.     

Computational Design of High Energy RDX-Based Derivatives: Property Prediction,Intermolecular Interactions,and Decomposition Mechanisms

A series of new high-energy insensitive compounds were designed based on 1,3,5-trinitro-1,3,5-triazinane (RDX) skeleton through incorporating -N(NO₂)-CH₂-N(NO₂)-, -N(NH₂)-, -N(NO₂)-, and -O- linkages. Then, their electronic structures, heats of formation, detonation properties, and impact sensitivities were analyzed and predicted using DFT. The types of intermolecular interactions between their bimolecular assemble were analyzed. The thermal decomposition of one compound with excellent performance was studied through ab initio molecular dynamics simulations. All the designed compounds exhibit excellent detonation properties superior to 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), and lower impact sensitivity than CL-20. Thus, they may be viewed as promising candidates for high energy density compounds. Overall, our design strategy that the construction of bicyclic or cage compounds based on the RDX framework through incorporating the intermolecular linkages is very beneficial for developing novel energetic compounds with excellent detonation performance and low sensitivity.     

Molecular dynamics study on the relationships of modeling, structural and energy properties with sensitivity for RDX-based PBXs

In this paper,a primary model is established for MD(molecular dynamics) simulation for the PBXs(polymer-bonded explosives) with RDX(cyclotrimethylene trinitramine) as base explosive and PS as polymer binder.A series of results from the MD simulation are compared between two PBX models,which are represented by PBX1 and PBX2,respectively,including one PS molecular chain having 46 repeating units and two PS molecular chains with each having 23 repeating units.It has been found that their structural,interaction energy and mechanical properties are basically consistent between the two models.A systematic MD study for the PBX2 is performed under NPT conditions at five different temperatures,i.e.,195 K,245 K,295 K,345 K,and 395 K.We have found that with the temperature increase,the maximum bond length(L max) of RDX N N trigger bond increases,and the interaction energy(E N-N) between two N atoms of the N-N trigger bond and the cohesive energy density(CED) decrease.These phenomena agree with the experimental fact that the PBX becomes more sensitive as the temperature increases.Therefore,we propose to use the maximum bond length L max of the trigger bond of the easily decomposed and exploded component and the interaction energy E N-N of the two relevant atoms as theoretical criteria to judge or predict the relative degree of heat and impact sensitivity for the energetic composites such as PBXs and solid propellants.     

The Adsorption Behavior of Gas Molecules on Co/N Co–Doped Graphene

Herein, we have used density functional theory (DFT) to investigate the adsorption behavior of gas molecules on Co/N₃ co–doped graphene (Co/N₃–gra). We have investigated the geometric stability, electric properties, and magnetic properties comprehensively upon the interaction between Co/N₃–gra and gas molecules. The binding energy of Co is −5.13 eV, which is big enough for application in gas adsorption. For the adsorption of C₂H₄, CO, NO₂, and SO₂ on Co/N–gra, the molecules may act as donors or acceptors of electrons, which can lead to charge transfer (range from 0.38 to 0.7 e) and eventually change the conductivity of Co/N–gra. The CO adsorbed Co/N₃–gra complex exhibits a semiconductor property and the NO₂/SO₂ adsorption can regulate the magnetic properties of Co/N₃–gra. Moreover, the Co/N₃–gra system can be applied as a gas sensor of CO and SO₂ with high stability. Thus, we assume that our results can pave the way for the further study of gas sensor and spintronic devices.     

Ortho-aryl substituted DPEphos ligands: rhodium complexes featuring C–H anagostic interactions and B–H agostic bonds

The synthesis of new Schrock–Osborn Rh(i) pre-catalysts with ortho-substituted DPEphos ligands, [Rh(DPEphos-R)(NBD)][BAr^F₄] [R = Me, OMe, ⁱPr; Ar^F = 3,5-(CF₃)₂C₆H₃], is described. Along with the previously reported R = H variant, variable temperature ¹H NMR spectroscopic and single-crystal X-ray diffraction studies show that these all have axial (C–H)⋯Rh anagostic interactions relative to the d⁸ pseudo square planar metal centres, that also result in corresponding downfield chemical shifts. Analysis by NBO, QTAIM and NCI methods shows these to be only very weak C–H⋯Rh bonding interactions, the magnitudes of which do not correlate with the observed chemical shifts. Instead, as informed by Scherer''s approach, it is the topological positioning of the C–H bond with regard to the metal centre that is important. For [Rh(DPEphos–ⁱPr)(NBD)][BAr^F₄] addition of H₂ results in a Rh(iii) ⁱPr–C–H activated product, [Rh(κ³,σ-P,O,P-DPEphos-ⁱPr′)(H)][BAr^F₄]. This undergoes H/D exchange with D₂ at the ⁱPr groups, reacts with CO or NBD to return Rh(i) products, and reaction with H₃B·NMe₃/tert-butylethene results in a dehydrogenative borylation to form a complex that shows both a non-classical B–H⋯Rh 3c-2e agostic bond and a C–H⋯Rh anagostic interaction at the same metal centre.

Rh(i) complexes of ortho-substituted DPEphos-R (R = H, Me, OMe, ⁱPr) ligands show anagostic interactions; for R =ⁱPr C–H activation/dehydrogenative borylation forms a product exhibiting both B–H/Rh 3c-2e agostic and C–H/Rh anagostic motifs.     

Facile conversion of ammonia to a nitride in a rhenium system that cleaves dinitrogen

Rhenium complexes with aliphatic PNP pincer ligands have been shown to be capable of reductive N₂ splitting to nitride complexes. However, the conversion of the resulting nitride to ammonia has not been observed. Here, the thermodynamics and mechanism of the hypothetical N–H bond forming steps are evaluated through the reverse reaction, conversion of ammonia to the nitride complex. Depending on the conditions, treatment of a rhenium(iii) precursor with ammonia gives either a bis(amine) complex [(PNP)Re(NH₂)₂Cl]⁺, or results in dehydrohalogenation to the rhenium(iii) amido complex, (PNP)Re(NH₂)Cl. The N–H hydrogen atoms in this amido complex can be abstracted by PCET reagents which implies that they are quite weak. Calorimetric measurements show that the average bond dissociation enthalpy of the two amido N–H bonds is 57 kcal mol⁻¹, while DFT computations indicate a substantially weaker N–H bond of the putative rhenium(iv)-imide intermediate (BDE = 38 kcal mol⁻¹). Our analysis demonstrates that addition of the first H atom to the nitride complex is a thermochemical bottleneck for NH₃ generation.

Rhenium–PNP complexes split N₂ to nitrides, but the nitrides do not give ammonia. Here, the thermodynamics of the hypothetical N–H bond forming steps are evaluated through the reverse reaction, showing that the first H addition is the bottleneck.     

Molecular dynamics simulations on the structures and properties of ε-CL-20-based PBXs——Primary theoretical studies on HEDM formulation design

Five polymer bonded explosives (PBXs) with the base explosiveε-CL-20 (hexanitrohexaazaisowurtzitane), the most important high energy density compound (HEDC), and five polymer binders (Estane 5703, GAP, HTPB, PEG, and F2314) were constructed. Molecular dynamics (MD) method was employed to investigate their binding energies (Ebind), compatibility, safety, mechanical properties, and energetic properties. The information and rules were reported for choosing better binders and guiding formulation design of high energy density material (HEDM). According to the calculated binding energies, the ordering of compatibility and stability of the five PBXs was predicted as ε-CL-20/PEG ＞ ε-CL-20/ Estane5703 ≈ε-CL-20/GAP ＞ ε-CL-20/HTPB ＞ ε-CL-20/F2314. By pair correlation function g(r) analyses, hydrogen bonds and vdw are found to be the main interactions between the two components. The elasticity and isotropy of PBXs based ε-CL-20 can be obviously improved more than pure ε-CL-20 crystal. It is not by changing the molecular structures of ε-CL-20 for each binder to affect the sensitivity. The safety and energetic properties of these PBXs are mainly influenced by the thermal capability (C°p) and density (ρ) of binders, respectively.     

Thermal behavior and decomposition kinetics of Formex-bonded explosives containing different cyclic nitramines

Thermal behavior and decomposition kinetics of Formex-bonded PBXs based on some attractive cyclic nitramines, such as 1,3,5-trinitro-1,3,5-triazinane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX). Actually, cis-1,3,4,6-tetranitrooctahy droimidazo-[4,5-d]imidazole (BCHMX) and 2,4,6,8,10,12-hexanitro-2,4,6,8,10, 12-hexaazaisowurtzitane (CL-20), was investigated by means of nonisothermal thermogravimetry (TG) and differential scanning calorimetry (DSC). It was found that the mass loss rate of PBXs involved in this research depends greatly on heating rate and the residue of the decomposition of these PBXs decreases with the heating rate. The onset of the exotherms was noticed at 215.4, 278.7, 231.2 and 233.7 °C with the peak maximum at 235.1, 279.0, 231.2 and 233.7 °C for RDX-Formex, HMX-Formex, CL-20-Formex, and BCHMX-Formex, respectively. Their corresponding exothermic changes were 1788, 1237, 691, and 1583 J g^?1. It was also observed that the dependence on the heating rate for onset temperatures of HMX- and BCHMX-based PBXs was almost the same due to their similar molecular structure. In addition, based on nonisothermal TG data, the kinetic parameters for thermal decomposition of these PBXs were calculated by isoconversional methods. It was shown that the Formex base has great effects on the activation energy distribution of nitramines. It was further found that the kinetic compensation effects occurred during the thermal decomposition of nitramine-based PBXs, and they almost have the same compensation effects due to similar decomposition mechanism.     

水分子对α相CL-20热分解机理影响的分子动力学研究

研究六硝基六氮杂异伍兹烷(CL-20)晶体不同晶型在不同温度下的反应机理, 对于深入认识含能材料在极端条件下的冲击起爆、冲击点火和爆轰过程等具有重要意义. 基于反应力场, 研究水分子在纯α相CL-20及其水合物的晶体结构中数量随时间的变换, 分析水分子对两种体系的初始分解和第二阶段的分解路径的影响. 计算结果表明: CL-20 分子的初始分解路径与水分子无关, 第二阶段的分解反应与水分子有关. 在低温(T<1500 K)下, 水分子对两种体系没有影响, 二者的初始分解路径均为N-NO₂键生成NO₂自由基; 在1500 K≤T≤2500 K时, 水分子作为反应物或与NO₂、、OH自由基等组成催化体系, 生成O₂、H₂O₂等产物, 加速水合物体系在高温下的第二阶段反应, 使得高温下水合物体系的化学反应速率和反应生成的NO₂自由基的数量比纯CL-20体系的化学反应速率和反应生成的NO₂自由基的数量大; 在T>2500 K时, 水分子的催化反应抑制CL-20初始分解反应, 使得在3000 K时纯CL-20体系的反应速率大于水合物体系中CL-20的反应速率.     

Cobalt(III) α-Dimethylglyoximates [Co(DH)2(Py)2]2SiF6 · 10H2O and [Co(DH)2(Thio)2]2SiF6 · 2H2O · C2H5OH: Synthesis and Structure

[Co(DH)₂(Py)₂]₂SiF₆ · 10H₂O and [Co(DH)₂(Thio)₂]₂SiF₆ · 2H₂O · C₂H₅OH complexes are synthesized and characterized by X-ray diffraction analysis. Two radicals of -glyoxime linked by hydrogen O–H···O bonds lie in the equatorial plane of the octahedral Co(III) complexes. Intramolecular (– and N–H···O) and intermolecular (O–H···F, O–H···O, N–H···F, N–H···O, N–H···S) interactions are discovered in the crystal. The influence of nonvalence interactions on the structures is discussed.     

N–H⋯X interactions stabilize intra-residue C5 hydrogen bonded conformations in heterocyclic α-amino acid derivatives

Nature makes extensive and elaborate use of hydrogen bonding to assemble and stabilize biomolecular structures. The shapes of peptides and proteins rely significantly on N–H⋯O C interactions, which are the linchpins of turns, sheets and helices. The C5 H-bond, in which a single residue provides both donor and acceptor, is generally considered too weak to force the backbone to adopt extended structures. Exploiting the synergy between gas phase (experimental and quantum chemistry) and solution spectroscopies to decipher IR spectroscopic data, this work demonstrates that the extended C5-based conformation in 4-membered ring heterocyclic α-amino acid derivatives is significantly stabilized by the formation of an N–H⋯X H-bond. In this synergic system the strength of the C5 interaction remains constant while the N–H⋯X H-bond strength, and thereby the support provided by it, varies with the heteroatom.

In 4-membered ring heterocyclic α-amino acid derivatives, extended conformations based on intraresidue C5 H-bonds can be stabilized by N–H⋯X H-bonds, making the combined C5–C6γ structures prominent in both gas phase and in weakly polar solutions.     

Anodic Processes Involving Trifluoromethyl Cobaloxime and Nucleophiles

Anodic oxidation of trifluoromethyl cobaloxime (CF₃)Co(DH)₂Py in the presence of such nucleophiles as pyridine or NO^– ₃ and C₆F₁₃COO^– anions is studied. A controlled-potential electrolysis and ¹⁹F NMR spectroscopy show the anodic reaction products to contain compounds with the bond >N–CF₃. A mechanism for the reaction between a labile Co(+4) complex and pyridine is offered. At potentials more positive than that of the Co(+3) Co(+4) oxidation, secondary products of electrochemical reaction form and are revealed by a cathodic reduction peak.     

Why heterogeneous single-atom catalysts preferentially produce CO in the electrochemical CO2 reduction reaction

Formate and CO are competing products in the two-electron CO₂ reduction reaction (2e CO₂RR), and they are produced via *OCHO and *COOH intermediates, respectively. However, the factors governing CO/formate selectivity remain elusive, especially for metal–carbon–nitrogen (M–N–C) single-atom catalysts (SACs), most of which produce CO as their main product. Herein, we show computationally that the selectivity of M–N–C SACs is intrinsically associated with the CO₂ adsorption mode by using bismuth (Bi) nanosheets and the Bi–N–C SAC as model catalysts. According to our results, the Bi–N–C SAC exhibits a strong thermodynamic preference toward *OCHO, but under working potentials, CO₂ is preferentially chemisorbed first due to a charge accumulation effect, and subsequent protonation of chemisorbed CO₂ to *COOH is kinetically much more favorable than formation of *OCHO. Consequently, the Bi–N–C SAC preferentially produces CO rather than formate. In contrast, the physisorption preference of CO₂ on Bi nanosheets contributes to high formate selectivity. Remarkably, this CO₂ adsorption-based mechanism also applies to other typical M–N–C SACs. This work not only resolves a long-standing puzzle in M–N–C SACs, but also presents simple, solid criteria (i.e., CO₂ adsorption modes) for indicating CO/formate selectivity, which help strategic development of high-performance CO₂RR catalysts.

This report discloses a nontrivial role of the CO₂ adsorption mode in governing the CO/formate selectivity of single-atom catalysts towards two-electron CO₂ reduction.     

Cross-dehydrogenative N–N couplings

The relatively high electronegativity of nitrogen makes N–N bond forming cross-coupling reactions particularly difficult, especially in an intermolecular fashion. The challenge increases even further when considering the case of dehydrogenative N–N coupling reactions, which are advantageous in terms of step and atom economy, but introduce the problem of the oxidant in order to become thermodynamically feasible. Indeed, the oxidizing system must be designed to activate the target N–H bonds, while at the same time avoid undesired N–N homocoupling as well as C–N and C–C coupled side products. Thus, preciously few intermolecular hetero N–N cross-dehydrogenative couplings exist, in spite of the central importance of N–N bonds in organic chemistry. This review aims at analyzing these few rare cases and provides a perspective for future developments.

For more than a century, the dehydrogenative formation of N–N bonds has remained mostly confidential. Several cross-dehydrogenative N–N coupling methods have appeared recently, promising a soon to come broad applicability of the concept.