Based on the full optimized molecular geometric structures via B3LYP/6-311＋G（2d,p） method, a new gem-dinitro energetic plasticizer, bis（2,2-dinitropropyl ethylene）formal was investigated in order to search for hi...Based on the full optimized molecular geometric structures via B3LYP/6-311＋G（2d,p） method, a new gem-dinitro energetic plasticizer, bis（2,2-dinitropropyl ethylene）formal was investigated in order to search for high-performance energetic material. IR spectrum, heat of formation, and detonation performances were predicted. The bond dissociation energies and bond orders for the weakest bonds were analyzed to investigate the thermal stability of the title compound. The results show that the four N-NO2 BDEs are nearly equal to the values of 164.38 kJ/mol, which shows that the title compound is a stable compound. The detonation velocity and pressure were evaluated by using Kamlet-Jacobs equations based on the theoretical density and condensed HOF. The crystal structure obtained by molec-ular mechanics belongs to P21 space group, with lattice parameters Z=2, a=13.8017 A, b=13.4072 A, c=5.5635 A.展开更多
Ab initio molecular orbital calculations have been performed at Hartree-Fock （HF）, second-order Mrller-Plesset （MP2）, and hybrid density functional theory （DFT） B3LYP levels with 6-31G^＊＊ basis set to investig...Ab initio molecular orbital calculations have been performed at Hartree-Fock （HF）, second-order Mrller-Plesset （MP2）, and hybrid density functional theory （DFT） B3LYP levels with 6-31G^＊＊ basis set to investigate the low sensitive explosive trans-1,4,5,8-tetranitro-1,4,5,8- tetraazadecalin （TNAD） and its seven bicyclic isomers. Their molecular geometries, electronic structures, thermodynamic properties, and detonation performances were predicted and compared. The relationships between structures and various properties were discussed in detail. The calculated results agree well with the available experimental data, and suggest that some compounds may be novel potential candidates of high energy density materials （HEDMs） with performances better than TNT （2,4,6-trinitrotoluene） and similar to RDX （1,3,5-trinitro-1,3,5-triazacyclohexane）.展开更多
The geometric structure, mechanism of detonation initiation and stability of transition metal carbohydrazide （CHZ） nitrates are investigated via density functional theory. The obtained results show that the Heyd-Scu...The geometric structure, mechanism of detonation initiation and stability of transition metal carbohydrazide （CHZ） nitrates are investigated via density functional theory. The obtained results show that the Heyd-Scuseria-Ernzerhof （HSE） functional yields the most accurate geometry. The initiating reaction of detonation in [Mn（CHZ）3]（NO3）2 and [Zn（CHZ）3]（NO3）2 is the formation of NO3 radicals. The calculated heat of formation and energy gap predict that the Mn and Zn complexes, which have the half-filled （3d5） and full-filled （3d10） electron configurations for the transition metal ions, respectively are more stable than the Co, Ni and Cu complexes. This indicates that the electron configuration of transition metal ion plays an important role in the stabilities of these energetic complexes.展开更多
The paper aims to theoretically and numerically investigate the confinement effect of inert materials on the detonation of insensitive high explosives. An improved shock polar theory based on the Zeldovich-von Neumann...The paper aims to theoretically and numerically investigate the confinement effect of inert materials on the detonation of insensitive high explosives. An improved shock polar theory based on the Zeldovich-von Neumann-Döring model of explosive detonation is established and can fully categorize the confinement interactions between insensitive high explosive and inert materials into six types for the inert materials with smaller sonic velocities than the Chapman-Jouguet velocity of explosive detonation. To confirm the theoretical categorization and obtain the flow details, a second-order, cell-centered Lagrangian hydrodynamic method based on the characteristic theory of the two-dimensional first-order hyperbolic partial differential equations with Ignition-Growth chemistry reaction law is proposed and can exactly numerically simulate the confinement interactions. The numerical result confirms the theoretical categorization and can further merge six types of interaction styles into five types for the inert materials with smaller sonic velocity, moreover, the numerical method can give a new type of interaction style existing a precursor wave in the confining inert material with a larger sonic velocity than the Chapman-Jouguet velocity of explosive detonation, in which a shock polar theory is invalid. The numerical method can also give the effect of inert materials on the edge angles of detonation wave front.展开更多
An expanding model of the confinement of non-ideal detonation of small charge is established on the basis of the nozzle theory.Making use of the expanding model,the analytic relationship of small charge detonation vel...An expanding model of the confinement of non-ideal detonation of small charge is established on the basis of the nozzle theory.Making use of the expanding model,the analytic relationship of small charge detonation velocity and the semi-empirical relationship of detonation pressure that both change with charge diameter and confinement condition are established.The detonation velocity and pressure of small charges are calculated and experimentally verified,and the detonation velocity deviation is less than 7% while the detonation pressure deviation is less than 9%.展开更多
Five fully optimized structures of complexes between aza-calix[6]arene host monomers（Ma～Me） and complexes（a～e） have been obtained at the B3LYP/6-31G（d） level.Natural bond orbital（NBO） analysis was performed ...Five fully optimized structures of complexes between aza-calix[6]arene host monomers（Ma～Me） and complexes（a～e） have been obtained at the B3LYP/6-31G（d） level.Natural bond orbital（NBO） analysis was performed to reveal the origin of the interaction.The intermolecular interaction energy was evaluated with basis set superposition error correction（BSSE） and zero point energy correction（ZPEC）.The B3LYP/6-31G（d） calculations on the five complexes have shown that the greatest interaction（–13.98 kJ/mol） is found in the complex between HMX and hexa-aza-calix[3]-p-tri-arene[3]-2-amido-1,3,5-tri-azine.The results have indicated that intermolecular interaction energies of aza-calix[6]arenes with substituted group are stronger than those without substituted group,and those with amido are greater than with nitryl.Thus,hexa-azacalix[3]-p-tri-arene[3]-2-amido-1,3,5-tri-azine is rather equal to eliminate HMX from explosive waste water.展开更多
In this paper,unsteady detonation is simulated and investigated from the viewpoint of kinetic theory.The deviations of the velocity distribution function from the equilibrium state are studied in the evolution of deto...In this paper,unsteady detonation is simulated and investigated from the viewpoint of kinetic theory.The deviations of the velocity distribution function from the equilibrium state are studied in the evolution of detonation.It has been discovered that the characteristics of the deviation around the detonation wave are significantly different from those in the post-wave region.Besides,the kinetic moments of the reaction term have been simulated,verified and analyzed in detail.In addition,the reaction manifestation is defined to describe the global effects of kinetic moments due to chemical reactions.It is interesting to find that there are three types of periodic oscillations of the reaction manifestation during the evolution of the unsteady detonation.Via the fast Fourier transform,it can be seen that the reaction manifestation is mainly composed of several signal frequencies.Moreover,the impact of rate constants of the two-step reaction scheme on the reaction manifestation is studied,and the influence of chemical heat is investigated as well.展开更多
基金ACKNOWLEDGMENTS This work was supported by the Key Project of Henan Educational Committee （No.12A140004）, China Postdoctoral Science Foundation （No.2013M531361）, and Jiangsu Planned Projects for Postdoctoral Research Funds （No.1201015B）.
文摘Based on the full optimized molecular geometric structures via B3LYP/6-311＋G（2d,p） method, a new gem-dinitro energetic plasticizer, bis（2,2-dinitropropyl ethylene）formal was investigated in order to search for high-performance energetic material. IR spectrum, heat of formation, and detonation performances were predicted. The bond dissociation energies and bond orders for the weakest bonds were analyzed to investigate the thermal stability of the title compound. The results show that the four N-NO2 BDEs are nearly equal to the values of 164.38 kJ/mol, which shows that the title compound is a stable compound. The detonation velocity and pressure were evaluated by using Kamlet-Jacobs equations based on the theoretical density and condensed HOF. The crystal structure obtained by molec-ular mechanics belongs to P21 space group, with lattice parameters Z=2, a=13.8017 A, b=13.4072 A, c=5.5635 A.
基金The project was supported by NNSFC (Nos. 10576030 and 10576016) and the Innovation Project for Postgraduates in the Universities of Jiangsu Province (AD20116)
文摘Ab initio molecular orbital calculations have been performed at Hartree-Fock （HF）, second-order Mrller-Plesset （MP2）, and hybrid density functional theory （DFT） B3LYP levels with 6-31G^＊＊ basis set to investigate the low sensitive explosive trans-1,4,5,8-tetranitro-1,4,5,8- tetraazadecalin （TNAD） and its seven bicyclic isomers. Their molecular geometries, electronic structures, thermodynamic properties, and detonation performances were predicted and compared. The relationships between structures and various properties were discussed in detail. The calculated results agree well with the available experimental data, and suggest that some compounds may be novel potential candidates of high energy density materials （HEDMs） with performances better than TNT （2,4,6-trinitrotoluene） and similar to RDX （1,3,5-trinitro-1,3,5-triazacyclohexane）.
基金supported by the National Natural Science Foundation of China(No.20471008)the Natural Science Foundation of Chongqing(No.cstc2011jjA50013)the Chongqing Municipal Commission of Education(No.KJ111310)
文摘The geometric structure, mechanism of detonation initiation and stability of transition metal carbohydrazide （CHZ） nitrates are investigated via density functional theory. The obtained results show that the Heyd-Scuseria-Ernzerhof （HSE） functional yields the most accurate geometry. The initiating reaction of detonation in [Mn（CHZ）3]（NO3）2 and [Zn（CHZ）3]（NO3）2 is the formation of NO3 radicals. The calculated heat of formation and energy gap predict that the Mn and Zn complexes, which have the half-filled （3d5） and full-filled （3d10） electron configurations for the transition metal ions, respectively are more stable than the Co, Ni and Cu complexes. This indicates that the electron configuration of transition metal ion plays an important role in the stabilities of these energetic complexes.
文摘The paper aims to theoretically and numerically investigate the confinement effect of inert materials on the detonation of insensitive high explosives. An improved shock polar theory based on the Zeldovich-von Neumann-Döring model of explosive detonation is established and can fully categorize the confinement interactions between insensitive high explosive and inert materials into six types for the inert materials with smaller sonic velocities than the Chapman-Jouguet velocity of explosive detonation. To confirm the theoretical categorization and obtain the flow details, a second-order, cell-centered Lagrangian hydrodynamic method based on the characteristic theory of the two-dimensional first-order hyperbolic partial differential equations with Ignition-Growth chemistry reaction law is proposed and can exactly numerically simulate the confinement interactions. The numerical result confirms the theoretical categorization and can further merge six types of interaction styles into five types for the inert materials with smaller sonic velocity, moreover, the numerical method can give a new type of interaction style existing a precursor wave in the confining inert material with a larger sonic velocity than the Chapman-Jouguet velocity of explosive detonation, in which a shock polar theory is invalid. The numerical method can also give the effect of inert materials on the edge angles of detonation wave front.
文摘An expanding model of the confinement of non-ideal detonation of small charge is established on the basis of the nozzle theory.Making use of the expanding model,the analytic relationship of small charge detonation velocity and the semi-empirical relationship of detonation pressure that both change with charge diameter and confinement condition are established.The detonation velocity and pressure of small charges are calculated and experimentally verified,and the detonation velocity deviation is less than 7% while the detonation pressure deviation is less than 9%.
文摘Five fully optimized structures of complexes between aza-calix[6]arene host monomers（Ma～Me） and complexes（a～e） have been obtained at the B3LYP/6-31G（d） level.Natural bond orbital（NBO） analysis was performed to reveal the origin of the interaction.The intermolecular interaction energy was evaluated with basis set superposition error correction（BSSE） and zero point energy correction（ZPEC）.The B3LYP/6-31G（d） calculations on the five complexes have shown that the greatest interaction（–13.98 kJ/mol） is found in the complex between HMX and hexa-aza-calix[3]-p-tri-arene[3]-2-amido-1,3,5-tri-azine.The results have indicated that intermolecular interaction energies of aza-calix[6]arenes with substituted group are stronger than those without substituted group,and those with amido are greater than with nitryl.Thus,hexa-azacalix[3]-p-tri-arene[3]-2-amido-1,3,5-tri-azine is rather equal to eliminate HMX from explosive waste water.
基金supported by the National Natural Science Foundation of China(under Grant No.51806116)Guangdong Basic and Applied Basic Research Foundation(under Grant No.2022A1515012116)。
文摘In this paper,unsteady detonation is simulated and investigated from the viewpoint of kinetic theory.The deviations of the velocity distribution function from the equilibrium state are studied in the evolution of detonation.It has been discovered that the characteristics of the deviation around the detonation wave are significantly different from those in the post-wave region.Besides,the kinetic moments of the reaction term have been simulated,verified and analyzed in detail.In addition,the reaction manifestation is defined to describe the global effects of kinetic moments due to chemical reactions.It is interesting to find that there are three types of periodic oscillations of the reaction manifestation during the evolution of the unsteady detonation.Via the fast Fourier transform,it can be seen that the reaction manifestation is mainly composed of several signal frequencies.Moreover,the impact of rate constants of the two-step reaction scheme on the reaction manifestation is studied,and the influence of chemical heat is investigated as well.
