2,6-双(二硝基亚甲基)-1,3,4,5,7,8-六硝基十二氢二咪唑[4,5-b:4',5'-e]吡嗪分子结构及性能的理论计算
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摘要
设计了一种新型高能量密度化合物2,6-双(二硝基亚甲基)-1,3,4,5,7,8-六硝基十二氢二咪唑[4,5-b:4',5'-e]吡嗪(DNNIP)。首先在B3PW91/6-31G++(d,p)水平下对目标分子进行优化,通过键长和键级的比较分析,判断母环的五元环侧链处N—NO2键为分解引发键,其键解离能是96.40 k J/mol;然后,基于静电势改进的蒙特卡洛法推测出该化合物的理论密度为2.07 g/cm3,采用等键反应计算出生成热为1 907.33 k J/mol,并进一步计算出DNNIP的爆速为10.35 km/s,爆压为51.47 GPa,爆轰性能明显优于现有常见含能材料。DNNIP的撞击感度为12 cm,与CL-20接近;能级差为0.158 78 a.u.(4.32 e V),光热稳定性较高,并且通过态密度分析认为硝基是分子中相对敏感位置。
A novel high energetic density compound,2,6-bis( dinitromethylidene)-1,3,4,5,7,8-hexanitrododecahydrodiimidazo[4,5-b: 4',5'-e]pyrazine( DNNIP),was designed. The molecular structure was firstly optimized under B3 PW91/6-31 G + +( d,p) level with Gaussian Software. After bond length and bond order analysis,it was found that decomposition would be initiated from the rupture of N—NO2 bond on imidazole ring with a bond dissociation enthalpy( BDE) of 96. 4 k J/mol. Its density was evaluated to be 2. 07 g/cm3 based on improved Monte Carlo method by electrostatic potential distribution,and formation heat was calculated as about 1907. 33 k J/mol from isodesmic reaction. From two parameters above,detonation velocity and pressure were calculated to be 10. 35 km/s and 51. 47 GPa,respectively,which were obviously better than those of common energetic materials. The evaluated impacting sensitivity of target compound having a significance in treatment is about 12 cm,which is close to that of CL-20. Energy gap between HOMO and LUMO[△E( LUMO-HOMO) ]is 0. 15878 a. u.( 4. 32 e V) indicating the stable molecular structure under general conditions.—NO2 is supposed to be located at the sensitive sites within molecular structure according to the density of state( DOS)analysis.
A novel high energetic density compound,2,6-bis( dinitromethylidene)-1,3,4,5,7,8-hexanitrododecahydrodiimidazo[4,5-b: 4',5'-e]pyrazine( DNNIP),was designed. The molecular structure was firstly optimized under B3 PW91/6-31 G + +( d,p) level with Gaussian Software. After bond length and bond order analysis,it was found that decomposition would be initiated from the rupture of N—NO2 bond on imidazole ring with a bond dissociation enthalpy( BDE) of 96. 4 k J/mol. Its density was evaluated to be 2. 07 g/cm3 based on improved Monte Carlo method by electrostatic potential distribution,and formation heat was calculated as about 1907. 33 k J/mol from isodesmic reaction. From two parameters above,detonation velocity and pressure were calculated to be 10. 35 km/s and 51. 47 GPa,respectively,which were obviously better than those of common energetic materials. The evaluated impacting sensitivity of target compound having a significance in treatment is about 12 cm,which is close to that of CL-20. Energy gap between HOMO and LUMO[△E( LUMO-HOMO) ]is 0. 15878 a. u.( 4. 32 e V) indicating the stable molecular structure under general conditions.—NO2 is supposed to be located at the sensitive sites within molecular structure according to the density of state( DOS)analysis.
引文
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[18]HAMMERL A,KLAPTKE T M,NTH H,et al.Synthesis,structure,molecular orbital and valence bond calculations for tetrazole azide,CHN7[J].Propellants,Exoplosives,Pyrotechnics,2003,28(4):165-173.
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[21]KAMLET M J,JACOBS S T.Chemistry of detonations.I.A simple method for calculating detonation properties of C-H-N-O explosives[J].The Journal of Chemical Physics,1968,48:23-35.
[22]POSPIL M,VVRA P,CONCHA M,et al.A possible crystal volume factor in the impact sensitivities of some energetic compounds[J].Journal of Molecular Modeling,2010,16(5):895-901.
[23]张君君.TNINA的合成与性能研究[D].南京:南京理工大学,2017.ZHANG J J.Study on synthesis and properties of TNINA[D].Nanjing:Nanjing University of Science&Technology,2017.
[2]GREENFIELD M,GUO Y Q,BERNSTEIN E R.Ultrafast photodissociation dynamics of HMX and RDX from their excited electronic states via femtosecond laser pumpprobe techniques[J].Chemical Physics Letters,2006,430(4/5/6):277-281.
[3]THOTTEMPUDI V,SHREEVE J M.Synthesis and promising properties of a new family of high-density energetic salts of 5-nitro-3-trinitromethyl-1H-1,2,4-triazole and 5,5'-bis(trinitromethyl)-3,3'-azo-1H-1,2,4-triazole[J].Journal of American Chemical Society,2011,133(49):19982-19992.
[4]KERTH J,LBBECKE S.Synthesis and characterization of 3,3'-azobis(6-amino-1,2,4,5-tetrazine)DAAT:a new promising nitrogen-rich compound[J].Propellants,Exoplosives,Pyrotechnics,2002,27(3):111-118.
[5]CHURAKOV A M,TARTAKOVSKY V A.Progress in1,2,3,4-tetrazine chemistry[J].Chemical Reviews,2004,104(5):2601-2616.
[6]CHO J R,KIM K J,CHO S G,et al.Synthesis and characterization of 1-methyl-2,4,5-trinitroimidazole(MTNI)[J].Journal of Heterocyclic Chemistry,2002,39(1):141-147.
[7]PAGORIA P F,LEE G S,MITCHELL A R,et al.A review of energetic materials synthesis[J].Thermochimica Acta,2002,384(1-2):187-204.
[8]XU W,AN C,WANG J,et al.Preparation and properties of an insensitive booster explosive based on LLM-105[J].Propellants,Exoplosives,Pyrotechnics,2013,38(1):136-141.
[9]SIKDER A K,SIKDER N.A review of advanced high performance,insensitive and thermally stable energetic materials emerging for military and space applications[J].Journal of Hazardous Materials,2004,112(1/2):1-15.
[10]QIU L,ZHU W H,XIAO J J,et al.Theoretical studies of solid bicyclo-HMX:effects of hydrostatic pressure and temperature[J].The Journal of Physical Chemistry B,2008,112(13):3882-3893.
[11]LIU Y,ZHANG L,WANG G X,et al.First-principle studies on the pressure-induced structural changes in energetic ionic salt 3-azido-1,2,4-triazolium nitrate crystal[J].The Journal of Physical Chemistry C,2012,116(30):16144-16153.
[12]高荣,陆明.2,4,7,9,11,14-六氮杂三环[8.4.0.03,8]十四烷的合成研究[J].含能材料,2002,10(2):53-55.GAO R,LU M.The Synthesis study of 2,4,7,9,11,14-hexazatricyclo[8.4.0.03,8]tetradecane[J].Chinese Journal of Energetic Materials,2002,10(2):53-55.
[13]ZHAO G,LU M.Comparative theoretical studies of energetic dodecahydrodiimidazo[4,5-b:4',5'-e]pyrazine derivatives[J].Computational and Theoretical Chemistry,2013,1007:57-62.
[14]王鹏程,陆明.1,3,4,5,7,8-六硝基八氢化二咪唑[4,5-b:4',5'-e]吡嗪-2,6-(1H,3H)-N,N'-二亚硝胺分子结构与性能的量子化学研究[J].高等学校化学学报,2014,35(3):596-601.WANG P C,LU M.Computational study on the chemical structure,explosive properties and sensitivity of N,N'-(1,3,4,5,7,8-hexanitrooctahydro-diimidazo[4,5-b:4',5'-e]pyrazine-2,6(1H,3H)-diylidene)dinitramide[J].Chemical Journal of Chinese Universities,2014,35(3):596-601.
[15]肖鹤鸣,朱卫华,肖继军,等.含能材料感度判别理论研究:从分子、晶体到复合材料[J].含能材料,2012,20(5):514-527.XIAO H M,ZHU W H,XIAO J J,et al.Theoretical studies on sensitivity criterion of energetic materials:from molecules,crystals,to composite materials[J].Chinese Journal of Energetic Materials,2012,20(5):514-527.
[16]肖鹤鸣,许晓娟,邱玲.高能量密度材料的理论设计[M].北京:科学出版社,2008.
[17]POLITZER P,MARTINEZ J,MURRAY J S,et al.An electrostatic interaction correction for improved crystal density prediction[J].Molecular Physics,2009,107(19):2095-2101.
[18]HAMMERL A,KLAPTKE T M,NTH H,et al.Synthesis,structure,molecular orbital and valence bond calculations for tetrazole azide,CHN7[J].Propellants,Exoplosives,Pyrotechnics,2003,28(4):165-173.
[19]DEAN J A.Lange’s handbook of chemistry[M].15th ed.New York:Mc Graw-Hill,1999.
[20]WILCOX C F,ZHANG Y X,BAUER S H.The thermochemistry of TNAZ(1,3,3-trinitroazetidine)and related species:models for calculating heats of formation[J].Journal of Molecular Structure:Theochem,2000,528(1/2/3):95-109.
[21]KAMLET M J,JACOBS S T.Chemistry of detonations.I.A simple method for calculating detonation properties of C-H-N-O explosives[J].The Journal of Chemical Physics,1968,48:23-35.
[22]POSPIL M,VVRA P,CONCHA M,et al.A possible crystal volume factor in the impact sensitivities of some energetic compounds[J].Journal of Molecular Modeling,2010,16(5):895-901.
[23]张君君.TNINA的合成与性能研究[D].南京:南京理工大学,2017.ZHANG J J.Study on synthesis and properties of TNINA[D].Nanjing:Nanjing University of Science&Technology,2017.