A deep understanding of explosive sensitivities and their factors is important for safe and reliable applications.However,quantitative prediction of the sensitivities is difficult.Here,reactive molecular dynamics simu...A deep understanding of explosive sensitivities and their factors is important for safe and reliable applications.However,quantitative prediction of the sensitivities is difficult.Here,reactive molecular dynamics simulation models for high-speed piston impacts on explosive supercells were established.Simulations were also performed to investigate shock-induced reactions of various high-energy explosives.The fraction of reacted explosive molecules in an initial supercell changed linearly with the propagation distance of the shock-wave front.The corresponding slope could be used as a reaction rate for a specific shock-loading velocity.Reaction rates that varied with the shock-loading pressure exhibited two-stage linearities with different slopes.The two inflection points corresponded to the initial and accelerated reactions,which respectively correlated to the thresholds of shock-induced ignition and detonation.Therefore,the ignition and detonation critical pressures could be determined.The sensitivity could then be a quantitative prediction of the critical pressure.The accuracies of the quantitative shock sensitivity predictions were verified by comparing the impact and shock sensitivities of common explosives and the characteristics of anisotropic shock-induced reactions.Molecular dynamics simulations quantitatively predict and rank shock sensitivities by using only crystal structures of the explosives.Overall,this method will enable the design and safe use of explosives.展开更多
Low-pressure air plasma cleaning is an effective method for removing organic contaminants on large-aperture optical components in situ in the inertial confinement fusion facility.Chemical reactions play a significant ...Low-pressure air plasma cleaning is an effective method for removing organic contaminants on large-aperture optical components in situ in the inertial confinement fusion facility.Chemical reactions play a significant role in plasma cleaning,which is a complex process involving abundant bond cleavage and species generation.In this work,experiments and reactive molecular dynamics simulations were carried out to unravel the reaction mechanism between the benchmark organic contaminants of dibutyl phthalate and air plasma.The optical emission spectroscopy was used to study the overall evolution behaviors of excited molecular species and radical signals from air plasma as a reference to simulations.Detailed reaction pathways were revealed and characterized,and specific intermediate radicals and products were analyzed during experiments and simulation.The reactive species in the air plasma,such as O,HO_(2)and O_(3)radicals,played a crucial role in cleaving organic molecular structures.Together,our findings provide an atomic-level understanding of complex reaction processes of low-pressure air plasma cleaning mechanisms and are essential for its application in industrial plasma cleaning.展开更多
Chemical inclusions significantly alter shock responses of crystalline explosives in macroscale gap experiments but their microscale dynamics origin remains unclear.Herein shock-induced energy localization,overall phy...Chemical inclusions significantly alter shock responses of crystalline explosives in macroscale gap experiments but their microscale dynamics origin remains unclear.Herein shock-induced energy localization,overall physical responses,and reactions in a-1,3,5-trinitro-1,3,5-triazinane(a-RDX)crystal entrained various chemical inclusions were investigated by the multi-scale shock technique implemented in the reactive molecular dynamics method.Results indicated that energy localization and shock reaction were affected by the intrinsic factors within chemical inclusions,i.e.,phase states,chemical compositions,and concentrations.The atomic origin of chemical-inclusions effects on energy localization is dependent on the dynamics mechanism of interfacial molecules with free space volume,which includes homogeneous intermolecular compression,interfacial impact and shear,and void collapse and jet.As introducing various chemical inclusions,the initiation of those dynamics mechanisms triggers diverse decay rates of bulk RDX molecules and hereby impacts on growth speeds of final reactions.Adding chemical inclusions can reduce the effectiveness of the void during the shock impacting.Under the shockwave velocity of 9 km/s,the parent RDX decay rate in RDX entrained amorphous carbon decreases the most and is about one fourth of that in RDX with a vacuum void,and solid HMX and TATB inclusions are more reactive than amorphous carbon but less reactive than dry air or acetone inclusions.The lessdense shocking system denotes the greater increases in local temperature and stress,the faster energy liberation,and the earlier final reaction into equilibrium,revealing more pronounced responses to the present intense shockwave.The quantitative models associated with the relative system density(RD_(sys))were proposed for indicating energy-localization mechanisms and evaluating initiation safety in the shocked crystalline explosive.RD_(sys)is defined by the density ratio of defective RDX to perfect crystal after dynamics relaxation and reveals the global density characteristic in shocked systems filled with chemical inclusions.When RD_(sys)is below 0.9,local hydrodynamic jet initiated by void collapse dominates upon energy localization instead of interfacial impact.This study sheds light on novel insights for understanding the shock chemistry and physical-based atomic origin in crystalline explosives considering chemical-inclusions effects.展开更多
Cold atmospheric plasma(CAP)has emerged as a promising technology for the degradation of organic dyes,but the underlying mechanisms at the molecular level remain poorly understood.Using density-functional tight-bindin...Cold atmospheric plasma(CAP)has emerged as a promising technology for the degradation of organic dyes,but the underlying mechanisms at the molecular level remain poorly understood.Using density-functional tight-binding(DFTB)-based quantum chemical molecular dynamics at 300 K,we have performed numerical simulations to investigate the degradation mechanism of Disperse Red 1(DR)interacting with CAP-generated oxygen radicals.One hundred directdynamics trajectories were calculated for up to 100 ps simulation time,after which hydrogenabstraction,benzene ring-opening/expanding,formaldehyde formation and modification in the chromophoric azo group which can lead to color-losing were observed.The latter was obtained with yields of around 6%at the given temperature.These findings not only enhance our understanding of CAP treatment processes but also have implications for the development of optimized purification systems for sustainable wastewater treatment.This study underscores the utility of DFTB simulations in unraveling complex chemical processes and guiding the design of advanced treatment strategies in the context of CAP technology.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.11832006).
文摘A deep understanding of explosive sensitivities and their factors is important for safe and reliable applications.However,quantitative prediction of the sensitivities is difficult.Here,reactive molecular dynamics simulation models for high-speed piston impacts on explosive supercells were established.Simulations were also performed to investigate shock-induced reactions of various high-energy explosives.The fraction of reacted explosive molecules in an initial supercell changed linearly with the propagation distance of the shock-wave front.The corresponding slope could be used as a reaction rate for a specific shock-loading velocity.Reaction rates that varied with the shock-loading pressure exhibited two-stage linearities with different slopes.The two inflection points corresponded to the initial and accelerated reactions,which respectively correlated to the thresholds of shock-induced ignition and detonation.Therefore,the ignition and detonation critical pressures could be determined.The sensitivity could then be a quantitative prediction of the critical pressure.The accuracies of the quantitative shock sensitivity predictions were verified by comparing the impact and shock sensitivities of common explosives and the characteristics of anisotropic shock-induced reactions.Molecular dynamics simulations quantitatively predict and rank shock sensitivities by using only crystal structures of the explosives.Overall,this method will enable the design and safe use of explosives.
基金the Joint Funds of National Natural Science Foundation of China and China Academy of Engineering Physics(NSAF)(No.U2030109)National Natural Science Foundation of China(No.52075129)。
文摘Low-pressure air plasma cleaning is an effective method for removing organic contaminants on large-aperture optical components in situ in the inertial confinement fusion facility.Chemical reactions play a significant role in plasma cleaning,which is a complex process involving abundant bond cleavage and species generation.In this work,experiments and reactive molecular dynamics simulations were carried out to unravel the reaction mechanism between the benchmark organic contaminants of dibutyl phthalate and air plasma.The optical emission spectroscopy was used to study the overall evolution behaviors of excited molecular species and radical signals from air plasma as a reference to simulations.Detailed reaction pathways were revealed and characterized,and specific intermediate radicals and products were analyzed during experiments and simulation.The reactive species in the air plasma,such as O,HO_(2)and O_(3)radicals,played a crucial role in cleaving organic molecular structures.Together,our findings provide an atomic-level understanding of complex reaction processes of low-pressure air plasma cleaning mechanisms and are essential for its application in industrial plasma cleaning.
基金the financial support from National Natural Science Foundation of China(Grant Nos.11872119,12172051,and 11972329)Natural Science Foundation of Hubei Province(Grant No.2021CFB120)。
文摘Chemical inclusions significantly alter shock responses of crystalline explosives in macroscale gap experiments but their microscale dynamics origin remains unclear.Herein shock-induced energy localization,overall physical responses,and reactions in a-1,3,5-trinitro-1,3,5-triazinane(a-RDX)crystal entrained various chemical inclusions were investigated by the multi-scale shock technique implemented in the reactive molecular dynamics method.Results indicated that energy localization and shock reaction were affected by the intrinsic factors within chemical inclusions,i.e.,phase states,chemical compositions,and concentrations.The atomic origin of chemical-inclusions effects on energy localization is dependent on the dynamics mechanism of interfacial molecules with free space volume,which includes homogeneous intermolecular compression,interfacial impact and shear,and void collapse and jet.As introducing various chemical inclusions,the initiation of those dynamics mechanisms triggers diverse decay rates of bulk RDX molecules and hereby impacts on growth speeds of final reactions.Adding chemical inclusions can reduce the effectiveness of the void during the shock impacting.Under the shockwave velocity of 9 km/s,the parent RDX decay rate in RDX entrained amorphous carbon decreases the most and is about one fourth of that in RDX with a vacuum void,and solid HMX and TATB inclusions are more reactive than amorphous carbon but less reactive than dry air or acetone inclusions.The lessdense shocking system denotes the greater increases in local temperature and stress,the faster energy liberation,and the earlier final reaction into equilibrium,revealing more pronounced responses to the present intense shockwave.The quantitative models associated with the relative system density(RD_(sys))were proposed for indicating energy-localization mechanisms and evaluating initiation safety in the shocked crystalline explosive.RD_(sys)is defined by the density ratio of defective RDX to perfect crystal after dynamics relaxation and reveals the global density characteristic in shocked systems filled with chemical inclusions.When RD_(sys)is below 0.9,local hydrodynamic jet initiated by void collapse dominates upon energy localization instead of interfacial impact.This study sheds light on novel insights for understanding the shock chemistry and physical-based atomic origin in crystalline explosives considering chemical-inclusions effects.
基金the financial support from the Ministry of Higher Education,Science,and Innovations of the Republic of Uzbekistan (Nos.AL-4821012320 and AL-5921122141)。
文摘Cold atmospheric plasma(CAP)has emerged as a promising technology for the degradation of organic dyes,but the underlying mechanisms at the molecular level remain poorly understood.Using density-functional tight-binding(DFTB)-based quantum chemical molecular dynamics at 300 K,we have performed numerical simulations to investigate the degradation mechanism of Disperse Red 1(DR)interacting with CAP-generated oxygen radicals.One hundred directdynamics trajectories were calculated for up to 100 ps simulation time,after which hydrogenabstraction,benzene ring-opening/expanding,formaldehyde formation and modification in the chromophoric azo group which can lead to color-losing were observed.The latter was obtained with yields of around 6%at the given temperature.These findings not only enhance our understanding of CAP treatment processes but also have implications for the development of optimized purification systems for sustainable wastewater treatment.This study underscores the utility of DFTB simulations in unraveling complex chemical processes and guiding the design of advanced treatment strategies in the context of CAP technology.
