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Title: A crossover in anisotropic nanomechanochemistry of van der Waals crystals

In nanoscale mechanochemistry, mechanical forces selectively break covalent bonds to essentially control chemical reactions. An archetype is anisotropic detonation of layered energetic molecular crystals bonded by van der Waals (vdW) interactions. Here, quantum molecular dynamics simulations reveal a crossover of anisotropic nanomechanochemistry of vdW crystal. Within 10{sup −13} s from the passage of shock front, lateral collision produces NO{sub 2} via twisting and bending of nitro-groups and the resulting inverse Jahn-Teller effect, which is mediated by strong intra-layer hydrogen bonds. Subsequently, as we transition from heterogeneous to homogeneous mechanochemical regimes around 10{sup −12} s, shock normal to multilayers becomes more reactive, producing H{sub 2}O assisted by inter-layer N-N bond formation. These time-resolved results provide much needed atomistic understanding of nanomechanochemistry that underlies a wider range of technologies.
Authors:
 [1] ;  [2] ;  [3] ;  [1] ;  [2] ;  [4] ; ; ;  [5] ;  [1]
  1. Department of Physics, Kumamoto University, Kumamoto 860-8555 (Japan)
  2. (United States)
  3. (Japan)
  4. Argonne Leadership Computing Facility, Argonne National Laboratory, Argonne, Illinois 60439 (United States)
  5. Collaboratory for Advanced Computing and Simulations, Department of Physics and Astronomy, Department of Computer Science, Department of Chemical Engineering and Materials Science, University of Southern California, Los Angeles, California 90089-0242 (United States)
Publication Date:
OSTI Identifier:
22486184
Resource Type:
Journal Article
Resource Relation:
Journal Name: Applied Physics Letters; Journal Volume: 107; Journal Issue: 23; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ANISOTROPY; CHEMICAL REACTIONS; COLLISIONS; HYDROGEN; JAHN-TELLER EFFECT; LAYERS; MOLECULAR CRYSTALS; MOLECULAR DYNAMICS METHOD; NANOSTRUCTURES; NITROGEN DIOXIDE; SIMULATION; TIME RESOLUTION; VAN DER WAALS FORCES