A crossover in anisotropic nanomechanochemistry of van der Waals crystals
Abstract
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 10−13 s from the passage of shock front, lateral collision produces NO2 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 10−12 s, shock normal to multilayers becomes more reactive, producing H2O 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.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Dec 07, 2015
- Source ID
- 10.1063/1.4937268
Entities
People
- Aiichiro Nakano
- Fuyuki Shimojo
- Kohei Shimamura
- Masaaki Misawa
- Priya Vashishta
- Rajiv K. Kalia
- Ying Li
Organizations
- Argonne National Laboratory
- Kobe University
- Kumamoto University
- Office of Naval Research
- University of Southern California