Molecular conformation evolutions of trans HNS under high pressure

Abstract

The molecular conformation evolution of Hexanitrostilbene (HNS) under high pressure was systematically investigated using Raman and Fourier transform infrared (FTIR) spectroscopy. The vibration modes of HNS associated with C-H, nitro groups, CC and the ring have been analyzed and clarified in detail under ambient conditions. trans-HNS is symmetrically distributed about –CHCH–, and six nitro groups are symmetrically distributed under ambient conditions. Two molecular conformation changes of HNS were observed at 1.4 GPa and 5 GPa due to the variations of hydrogen-bond interaction between C-H (in the ring) and N-O and the distortion of trans olefin, respectively. The hydrogen-bond interaction between C-H (in the ring) and N-O strengthened at 1.4 GPa. It induced the degenerated symmetry of the nitro groups and the Raman changes of νas (NO2), ν(CC), ν(C-C) and ν(C-H). In addition, the nonplanarity property of HNS and the sensitivity of trans olefin to pressure promoted the deformation of trans olefin, as well as the hydrogen bond interaction between C-H (in trans olefin) and N-O at about 5 GPa. When further loading pressure on HNS, the variations in the hydrogen-bond interaction between C-H and N-O restricted the vibrations of C-H, NO2 and the ring. It blocked the nonradiative pathway and activated the strong fluorescent background in the Raman spectra as the pressure increased above 5.7 GPa. These current results reveal that there is no structural transformation and only conformational changes under high pressure for HNS.