Shock Wave-Induced Chemical Decomposition of RDX Crystals

ORAL

Abstract

Time-resolved optical spectroscopy and quantum chemistry calculations were combined to gain insight into molecular processes in shock-induced decomposition of RDX. Crystals of [111] orientation were shocked to peak stresses between 7.0 and 20.0 GPa. Broadband light emission was observed over the range of 350 - 850 nm with a threshold in spectral behavior at about 10 GPa. Below this threshold, the spectral profile remained unchanged during the experiment. Above 10 GPa, the emission spectrum changed with time and shifted to longer wavelengths. Based on these observations and quantum calculations, the emission spectrum was assigned to NO$_{2}$ radicals and HONO intermediates. Unimolecular decomposition of RDX leads to the production of these species through multiple decomposition steps. The observed threshold behavior is proposed to be due to the onset of bimolecular reactions between radical decomposition products and unreacted RDX molecules. We put forward a full decomposition scheme consistent with the main observations from our spectroscopy experiments. This work demonstrates the value of combining spectroscopy experiments with first principles calculations to understand decomposition of HE crystals.

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Authors

  • Zbigniew Dreger

    Institute for Shock Physics, Washington State University

  • J.P. Escobedo

    Naval Research Enterprise Intern Program, Los Alamos National Laboratory, Los Alamos, USA, RFNC, All-Russia Research Institute of Experimental Physics, Sarov, Russia, University of Oxford, Lawrence Livermore National Laboratory, AWE, Department of Electrical and Electronic Engineering, National Defense Academy of Japan, Japan Synchrotron Radiation Research Institute / SPring-8, Division of Electrical, Electronic and Information Engineering, Osaka University, Division of Materials and Manufacturing Science, Osaka University, University of Illinois, RAFAEL, P. O. Box 2250, Haifa, Israel, Faculty of Mechanical Engineering, Technion - Israel Institute of Technology, 32000, Haifa, Israel, LANL, Fracture and Shock Physics, SMF Group, Cavendish Laboratory, JJ Thomson Ave., Cambridge, CB3 0HE, QinetiQ Ltd., Fort Halstead, Sevenoaks, Kent, TN14 7BP, UK, ILE, Osaka University, SPring-8, Lawrence Livermore National Lab., CEA, LULI, Ecole Polytechnique, Graduate School of Engineering, Osaka University, LLNL, Livermore, USA, LLE, Rocherster, USA, Graduate school of engineering, Osaka university, Suita, Osaka , Japan, LULI, Ecole polytechnique, Palaiseau, France, Georgia Institute of Technology, Shocks Unlimited, Los Alamos National Laboratory, Air Force Research Laboratory, Naval Surface Warfare Center, Institute for Shock Physics, Washington State University, Institute of Applied Physics and Computational Mathematics, Beijing, China, Institute of Applied Physics and Computational Mathematics, China, General Atomics, San Diego, CA, Fraunhofer Institute, Freiburg, Germany, LLNL, Harvard University, Corvid Technologies, IPCP RAS, Academy of Sciences of the Czech Republic, Institute of Physics of Materials and Los Alamos National Laboratory, Theoretical Division, QinetiQ, Department of Chemistry, University of Missouri-Columbia, Theoretical Division, Los Alamos National Laboratory, Theoretical Division, Los Alamos National Lab, Vanderbilt University, Laboratory for Shock Wave and Detonation Physics Research, Institute of Fluid Physics, Ioffe PTI RAS, Sandia National Laboratories, LCD-CNRS (UPR 9028), Institute for Shock Physics, Washington State University, Pullman, WA 99164-2816, CEA/DAM/DIF F91297 Arpajon, France, Russian Academy of Science, The First Aeronautic Institute of the Air Force, NSWC Dahlgren Division, ICMM UB RAS, Saitama Inst. Tech, Tohoku Univ., Sarov Laboratories, Carnegie Institution of Washington, National Institute of Standards and Technology, Universidad de Puerto Rico, National Institute for Materials Science, Japan, Shock Wave and Condensed Matter Research Center, Kumamoto University, Japan, Institute of Laser Engineering, Osaka University, Japan, Division of Electrical, Electronic and Information Engineering, Institute of Laser Engineering, Osaka University, Japan, Division of Electrical, Electronic and Information Engineering, Osaka University, Japan, Division of Materials and Manufacturing Science, Osaka University, Japan, LANL, USA, RFNC-VNIIEF, Cranfield University, LMPM ENSMA - CNRS, LCD ENSMA - CNRS, CEA Valduc, Laboratoire de Combustion et de Detonique (UPR 9028), ENSMA, Futuroscope, France, Laboratoire de Min\'eralogie (UMR 75-90), IMPMC, Paris, France, DPTA, CEA/DAM, Bruy\`eres-le-Ch\^atel, France, Centre for Astrophysics and Planetary Science, School of Physical Sciences, University of Kent, Canterbury, IARC, Dept. of Mineralogy, Natural History Museum, London, UK, Institute of Fluid Physics, CAEP, University of Missouri, Dept. of Mechanical and Aerospace Engineering, University of California at San Diego, La Jolla, CA 92093-0411, School of Materials Science and Engineering, Georgia Tech, Atlanta, GA 30332-0245, Lawrence Livermore National Laboratory, Physical Life Sciences, Livermore, California 94551, University of Cambridge, IHED RAS, ITT, Marquette University, Naval Surface Warfare Center, Carderock Division, Naval Surface Warfare Center, Dahlgren Division, Faculty of Science, Beijing University of Chemical Technology, Beijing 100029, China, ADAI, University of Coimbra, U.S. Army ARDEC, Naval Research Laboratory, Physics Department, USF, Ball Aerospace \& Technologies Corp., Joint Institute for High Temperatures RAS, Moscow, Russia, Institut fur Theoretische Physik und Astrophysik, Kiel, Germany, LALP, Sandia National Laboratories, New Mexico, PO Box 5800, Albuquerque, NM 87185-1454, Stanford University, Civil and Environmental Engineering Department, Palo Alto, California 94305, GEA Barr-Rosin Ltd., 48 Bell St., Maidenhead, SL6 1BR, UK, Russian Federal Nuclear Center,VNIIEF, Sarov, Russia, University of Maryland, College Park, Maryland 20742, University of Bayreuth, Germany, Royal Institute of Technology, Sweden, Energetic Materials Center, Lawrence Livermore National Laboratory, Livermore, CA 94550, IHDIV, NSWC, US Army Research Laboratory, beijing Institute of technology, University of Science \& Technology of China, Grad. Sch. Sci. and Engn., Tokyo Inst. Tech., ILE, Osaka Univ., Center for Quantum Science and Technology under Extreme Conditions, Osaka Univ., Inst. for Study of The Earth's Interior, Okayama Univ., Grad. Sch. Engn., Osaka Univ., National Key Laboratory for Shock Wave and Detonation Physics, Institute of Fluid Physics, People's Republic of China, Energetic Materials Center, Lawrence Livermore National Laboratory, AFRL/RXLMD Wright-Patterson AFB, OH, AFRL/RWME Eglin AFB, FL, AFRL/RWME, Institute of High Performance Computing, Singapore, School of Physical Sciences, University of Kent, Canterbury, UK, LZ Technology/ECSG, Johnson Space Centre, Houston, TX, USA, IARC, Dept. of Mineralogy, The Natural History Museum, London, UK, Mullard Space Science Laboratory, UK, Qiniteq, UK, JIHT RAS, Rutherford Appleton Laboratory, Science and Technology Facilities Council, AWE, Aldermaston, Reading, RG7 4PR, UK, CNRS-LALP, Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125 U.S.A., U.S. Army Research Office, RTP, NC 27709-2211, Institute of Problems of Chemical Physics, Chernogolovka, Russia, Department of Physics, Harvard University, Cambridge, MA 02138, AWE plc, CEA, DAM, CESTA, CEA, DAM, DIF, CEA, DAM, VALDUC, Leatherhead Foods International, Lawrence-Livermore Nat. Lab., Wash. State Univ., Institute of Applied Physics and Computational Mathematics, Beijing, 100094, China

  • J.P. Escobedo

    Naval Research Enterprise Intern Program, Los Alamos National Laboratory, Los Alamos, USA, RFNC, All-Russia Research Institute of Experimental Physics, Sarov, Russia, University of Oxford, Lawrence Livermore National Laboratory, AWE, Department of Electrical and Electronic Engineering, National Defense Academy of Japan, Japan Synchrotron Radiation Research Institute / SPring-8, Division of Electrical, Electronic and Information Engineering, Osaka University, Division of Materials and Manufacturing Science, Osaka University, University of Illinois, RAFAEL, P. O. Box 2250, Haifa, Israel, Faculty of Mechanical Engineering, Technion - Israel Institute of Technology, 32000, Haifa, Israel, LANL, Fracture and Shock Physics, SMF Group, Cavendish Laboratory, JJ Thomson Ave., Cambridge, CB3 0HE, QinetiQ Ltd., Fort Halstead, Sevenoaks, Kent, TN14 7BP, UK, ILE, Osaka University, SPring-8, Lawrence Livermore National Lab., CEA, LULI, Ecole Polytechnique, Graduate School of Engineering, Osaka University, LLNL, Livermore, USA, LLE, Rocherster, USA, Graduate school of engineering, Osaka university, Suita, Osaka , Japan, LULI, Ecole polytechnique, Palaiseau, France, Georgia Institute of Technology, Shocks Unlimited, Los Alamos National Laboratory, Air Force Research Laboratory, Naval Surface Warfare Center, Institute for Shock Physics, Washington State University, Institute of Applied Physics and Computational Mathematics, Beijing, China, Institute of Applied Physics and Computational Mathematics, China, General Atomics, San Diego, CA, Fraunhofer Institute, Freiburg, Germany, LLNL, Harvard University, Corvid Technologies, IPCP RAS, Academy of Sciences of the Czech Republic, Institute of Physics of Materials and Los Alamos National Laboratory, Theoretical Division, QinetiQ, Department of Chemistry, University of Missouri-Columbia, Theoretical Division, Los Alamos National Laboratory, Theoretical Division, Los Alamos National Lab, Vanderbilt University, Laboratory for Shock Wave and Detonation Physics Research, Institute of Fluid Physics, Ioffe PTI RAS, Sandia National Laboratories, LCD-CNRS (UPR 9028), Institute for Shock Physics, Washington State University, Pullman, WA 99164-2816, CEA/DAM/DIF F91297 Arpajon, France, Russian Academy of Science, The First Aeronautic Institute of the Air Force, NSWC Dahlgren Division, ICMM UB RAS, Saitama Inst. Tech, Tohoku Univ., Sarov Laboratories, Carnegie Institution of Washington, National Institute of Standards and Technology, Universidad de Puerto Rico, National Institute for Materials Science, Japan, Shock Wave and Condensed Matter Research Center, Kumamoto University, Japan, Institute of Laser Engineering, Osaka University, Japan, Division of Electrical, Electronic and Information Engineering, Institute of Laser Engineering, Osaka University, Japan, Division of Electrical, Electronic and Information Engineering, Osaka University, Japan, Division of Materials and Manufacturing Science, Osaka University, Japan, LANL, USA, RFNC-VNIIEF, Cranfield University, LMPM ENSMA - CNRS, LCD ENSMA - CNRS, CEA Valduc, Laboratoire de Combustion et de Detonique (UPR 9028), ENSMA, Futuroscope, France, Laboratoire de Min\'eralogie (UMR 75-90), IMPMC, Paris, France, DPTA, CEA/DAM, Bruy\`eres-le-Ch\^atel, France, Centre for Astrophysics and Planetary Science, School of Physical Sciences, University of Kent, Canterbury, IARC, Dept. of Mineralogy, Natural History Museum, London, UK, Institute of Fluid Physics, CAEP, University of Missouri, Dept. of Mechanical and Aerospace Engineering, University of California at San Diego, La Jolla, CA 92093-0411, School of Materials Science and Engineering, Georgia Tech, Atlanta, GA 30332-0245, Lawrence Livermore National Laboratory, Physical Life Sciences, Livermore, California 94551, University of Cambridge, IHED RAS, ITT, Marquette University, Naval Surface Warfare Center, Carderock Division, Naval Surface Warfare Center, Dahlgren Division, Faculty of Science, Beijing University of Chemical Technology, Beijing 100029, China, ADAI, University of Coimbra, U.S. Army ARDEC, Naval Research Laboratory, Physics Department, USF, Ball Aerospace \& Technologies Corp., Joint Institute for High Temperatures RAS, Moscow, Russia, Institut fur Theoretische Physik und Astrophysik, Kiel, Germany, LALP, Sandia National Laboratories, New Mexico, PO Box 5800, Albuquerque, NM 87185-1454, Stanford University, Civil and Environmental Engineering Department, Palo Alto, California 94305, GEA Barr-Rosin Ltd., 48 Bell St., Maidenhead, SL6 1BR, UK, Russian Federal Nuclear Center,VNIIEF, Sarov, Russia, University of Maryland, College Park, Maryland 20742, University of Bayreuth, Germany, Royal Institute of Technology, Sweden, Energetic Materials Center, Lawrence Livermore National Laboratory, Livermore, CA 94550, IHDIV, NSWC, US Army Research Laboratory, beijing Institute of technology, University of Science \& Technology of China, Grad. Sch. Sci. and Engn., Tokyo Inst. Tech., ILE, Osaka Univ., Center for Quantum Science and Technology under Extreme Conditions, Osaka Univ., Inst. for Study of The Earth's Interior, Okayama Univ., Grad. Sch. Engn., Osaka Univ., National Key Laboratory for Shock Wave and Detonation Physics, Institute of Fluid Physics, People's Republic of China, Energetic Materials Center, Lawrence Livermore National Laboratory, AFRL/RXLMD Wright-Patterson AFB, OH, AFRL/RWME Eglin AFB, FL, AFRL/RWME, Institute of High Performance Computing, Singapore, School of Physical Sciences, University of Kent, Canterbury, UK, LZ Technology/ECSG, Johnson Space Centre, Houston, TX, USA, IARC, Dept. of Mineralogy, The Natural History Museum, London, UK, Mullard Space Science Laboratory, UK, Qiniteq, UK, JIHT RAS, Rutherford Appleton Laboratory, Science and Technology Facilities Council, AWE, Aldermaston, Reading, RG7 4PR, UK, CNRS-LALP, Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125 U.S.A., U.S. Army Research Office, RTP, NC 27709-2211, Institute of Problems of Chemical Physics, Chernogolovka, Russia, Department of Physics, Harvard University, Cambridge, MA 02138, AWE plc, CEA, DAM, CESTA, CEA, DAM, DIF, CEA, DAM, VALDUC, Leatherhead Foods International, Lawrence-Livermore Nat. Lab., Wash. State Univ., Institute of Applied Physics and Computational Mathematics, Beijing, 100094, China

  • J.P. Escobedo

    Naval Research Enterprise Intern Program, Los Alamos National Laboratory, Los Alamos, USA, RFNC, All-Russia Research Institute of Experimental Physics, Sarov, Russia, University of Oxford, Lawrence Livermore National Laboratory, AWE, Department of Electrical and Electronic Engineering, National Defense Academy of Japan, Japan Synchrotron Radiation Research Institute / SPring-8, Division of Electrical, Electronic and Information Engineering, Osaka University, Division of Materials and Manufacturing Science, Osaka University, University of Illinois, RAFAEL, P. O. Box 2250, Haifa, Israel, Faculty of Mechanical Engineering, Technion - Israel Institute of Technology, 32000, Haifa, Israel, LANL, Fracture and Shock Physics, SMF Group, Cavendish Laboratory, JJ Thomson Ave., Cambridge, CB3 0HE, QinetiQ Ltd., Fort Halstead, Sevenoaks, Kent, TN14 7BP, UK, ILE, Osaka University, SPring-8, Lawrence Livermore National Lab., CEA, LULI, Ecole Polytechnique, Graduate School of Engineering, Osaka University, LLNL, Livermore, USA, LLE, Rocherster, USA, Graduate school of engineering, Osaka university, Suita, Osaka , Japan, LULI, Ecole polytechnique, Palaiseau, France, Georgia Institute of Technology, Shocks Unlimited, Los Alamos National Laboratory, Air Force Research Laboratory, Naval Surface Warfare Center, Institute for Shock Physics, Washington State University, Institute of Applied Physics and Computational Mathematics, Beijing, China, Institute of Applied Physics and Computational Mathematics, China, General Atomics, San Diego, CA, Fraunhofer Institute, Freiburg, Germany, LLNL, Harvard University, Corvid Technologies, IPCP RAS, Academy of Sciences of the Czech Republic, Institute of Physics of Materials and Los Alamos National Laboratory, Theoretical Division, QinetiQ, Department of Chemistry, University of Missouri-Columbia, Theoretical Division, Los Alamos National Laboratory, Theoretical Division, Los Alamos National Lab, Vanderbilt University, Laboratory for Shock Wave and Detonation Physics Research, Institute of Fluid Physics, Ioffe PTI RAS, Sandia National Laboratories, LCD-CNRS (UPR 9028), Institute for Shock Physics, Washington State University, Pullman, WA 99164-2816, CEA/DAM/DIF F91297 Arpajon, France, Russian Academy of Science, The First Aeronautic Institute of the Air Force, NSWC Dahlgren Division, ICMM UB RAS, Saitama Inst. Tech, Tohoku Univ., Sarov Laboratories, Carnegie Institution of Washington, National Institute of Standards and Technology, Universidad de Puerto Rico, National Institute for Materials Science, Japan, Shock Wave and Condensed Matter Research Center, Kumamoto University, Japan, Institute of Laser Engineering, Osaka University, Japan, Division of Electrical, Electronic and Information Engineering, Institute of Laser Engineering, Osaka University, Japan, Division of Electrical, Electronic and Information Engineering, Osaka University, Japan, Division of Materials and Manufacturing Science, Osaka University, Japan, LANL, USA, RFNC-VNIIEF, Cranfield University, LMPM ENSMA - CNRS, LCD ENSMA - CNRS, CEA Valduc, Laboratoire de Combustion et de Detonique (UPR 9028), ENSMA, Futuroscope, France, Laboratoire de Min\'eralogie (UMR 75-90), IMPMC, Paris, France, DPTA, CEA/DAM, Bruy\`eres-le-Ch\^atel, France, Centre for Astrophysics and Planetary Science, School of Physical Sciences, University of Kent, Canterbury, IARC, Dept. of Mineralogy, Natural History Museum, London, UK, Institute of Fluid Physics, CAEP, University of Missouri, Dept. of Mechanical and Aerospace Engineering, University of California at San Diego, La Jolla, CA 92093-0411, School of Materials Science and Engineering, Georgia Tech, Atlanta, GA 30332-0245, Lawrence Livermore National Laboratory, Physical Life Sciences, Livermore, California 94551, University of Cambridge, IHED RAS, ITT, Marquette University, Naval Surface Warfare Center, Carderock Division, Naval Surface Warfare Center, Dahlgren Division, Faculty of Science, Beijing University of Chemical Technology, Beijing 100029, China, ADAI, University of Coimbra, U.S. Army ARDEC, Naval Research Laboratory, Physics Department, USF, Ball Aerospace \& Technologies Corp., Joint Institute for High Temperatures RAS, Moscow, Russia, Institut fur Theoretische Physik und Astrophysik, Kiel, Germany, LALP, Sandia National Laboratories, New Mexico, PO Box 5800, Albuquerque, NM 87185-1454, Stanford University, Civil and Environmental Engineering Department, Palo Alto, California 94305, GEA Barr-Rosin Ltd., 48 Bell St., Maidenhead, SL6 1BR, UK, Russian Federal Nuclear Center,VNIIEF, Sarov, Russia, University of Maryland, College Park, Maryland 20742, University of Bayreuth, Germany, Royal Institute of Technology, Sweden, Energetic Materials Center, Lawrence Livermore National Laboratory, Livermore, CA 94550, IHDIV, NSWC, US Army Research Laboratory, beijing Institute of technology, University of Science \& Technology of China, Grad. Sch. Sci. and Engn., Tokyo Inst. Tech., ILE, Osaka Univ., Center for Quantum Science and Technology under Extreme Conditions, Osaka Univ., Inst. for Study of The Earth's Interior, Okayama Univ., Grad. Sch. Engn., Osaka Univ., National Key Laboratory for Shock Wave and Detonation Physics, Institute of Fluid Physics, People's Republic of China, Energetic Materials Center, Lawrence Livermore National Laboratory, AFRL/RXLMD Wright-Patterson AFB, OH, AFRL/RWME Eglin AFB, FL, AFRL/RWME, Institute of High Performance Computing, Singapore, School of Physical Sciences, University of Kent, Canterbury, UK, LZ Technology/ECSG, Johnson Space Centre, Houston, TX, USA, IARC, Dept. of Mineralogy, The Natural History Museum, London, UK, Mullard Space Science Laboratory, UK, Qiniteq, UK, JIHT RAS, Rutherford Appleton Laboratory, Science and Technology Facilities Council, AWE, Aldermaston, Reading, RG7 4PR, UK, CNRS-LALP, Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125 U.S.A., U.S. Army Research Office, RTP, NC 27709-2211, Institute of Problems of Chemical Physics, Chernogolovka, Russia, Department of Physics, Harvard University, Cambridge, MA 02138, AWE plc, CEA, DAM, CESTA, CEA, DAM, DIF, CEA, DAM, VALDUC, Leatherhead Foods International, Lawrence-Livermore Nat. Lab., Wash. State Univ., Institute of Applied Physics and Computational Mathematics, Beijing, 100094, China