| Energetic materials are widely used in many fields,sunch as national defense security,economic construction and social development.Research on energetic materials has been focused on how to improve the detonation performance under the premise of ensuring safety.Energetic material molecules are mainly organic molecules based on CNHO.There are not only weak intermolecular nonbond but also strong intramolecular bonding,and there are strong coupling between them.In this paper,we will expend the hydrogen bond coordination relaxation theory of ice water,and explore the mechanism of inter-and intramolecular bond cooperation in the energetic materials by high temperature and pressure Raman spectroscopy and differential phonon spectroscopy.Extension of the Grüneisen parameters integrates the phonon frequency shift to the intrinsic compressibility,thermal expansibility,specific heat,equilibrium bond length,atomic cohesive energy,and bonding energy density of the single bond which represents all its sorts contributing to the spectral peak.So as provide a possible theoretical guidance for the regulation of the sensitivity and ferocity of energetic materials.The main research contents and results are as follows:（1）Intermolecular bonding of NM/H2O mixed solution:Based on the theory of hydrogen bonds segmented cooperative relaxation,molecular strong polarization and differential phonon spectroscopy,combined with Raman spectroscopy,coherent anti Stokes Raman（CARS）and ultrafast Brilouin scattering technology,the applicability of hydrogen bond segmented cooperative relaxation in the hydrogen bond structure of NM/H2O solution and the frequency shift change of characteristic vibration modes of NM and H2O caused by intermolecular strong polarization are explored.In addition,by comparing the phonon lifetime and the sound velocity of solute and solvent,the intermolecular bond interaction and strong polarization are confirmed.（2）Interactions between NM molecules:The relaxation process of the characteristic vibrational modes C—H,N—O,C—N and X:H bond of NM molecules was observed by high temperature and pressure Raman spectroscopy.It is clear that hydrogen bond segmental relaxation and super-HB repulsion mediate the change of characteristic frequency.At high temperature,the X:H nonbond in the X:H—C hydrogen bond between NM molecules expands and the C—H covalent bond compresses abnormally,which is the same as the thermal relaxation mode of O:H—O hydrogen bond in ice water.Under high pressure,the Coulomb repulsion force between C—H is insufficient,resulting in comprssion of both X:H and H—C segments.The covalent bonds of N—O and C—N follow the regular law of thermal expansion and compression contraction.In addition,the Grüneisen parameter is extended by bond relaxation theory,the good prediction of the experimental results is made.（3）Interactions between TATB molecules:TATB is a typical insensitive explosive.The high temperature and pressure Raman spectra of TATB have been studied,and the mechanism of molecular bonding interaction of TATB has been clarified.At high temperature,X:H nonbond elongates,H—N covalent bond compresses abnormally;at high pressure,X:H nonbond shortens,H—N covalent bond expands abnormally.Under the stimulation of high temperature and pressure,the relaxation mode of X:H—N hydrogen bond is the same as that of ice water O:H—O.The strong repulsion force of X:（?）:Y（X,Y=N,O）super-HB cause other covalent bonds to show a similar regular thermal expansion and compression contraction law at high temperature or pressure.Only when the mechanism of inter-and intramolecular interaction is clear,can the sensitivity and ferocity of TATB nitroenergetic materials be better regulated. |
