MRS Proceedings


Modeling of Early Stages of Formation of Poly-CO

2011 MRS Fall Meeting.

I. G. Batyreva1, W. D. Mattsona1 and B. M. Ricea1

a1 US Army Research Laboratory, Aberdeen Proving Ground, Maryland


We studied the early stages of polymerization of CO under pressure. We performed DFT simulations of 128 and 432 atom models. Structures of random networks found at zero temperature were used for equilibration at 100 K by employing first principles MD. We found that the polymerization begins at 7 - 8 GPa and slightly depends on the size of the model. It turned out that there are several metastable phases of the extended CO solid, corresponding to different compression pressures from 7 - 8 GPa to 15-18 GPa with different numbers of CO fragments, not connected to the random network. We also found that the transition to the phases is irreversible which results in hysteresis loops. Random network structures obtained, say, under 18 GPa could exist at 3 GPa, whereas compression to 3 GPa results in the delta phase of CO crystal, with intact CO fragments and minor distortion of the cubic phase. To analyze the random structure fragments we calculated normal modes and IR intensities using the dipole approximation. Contributions from the main motifs of the random network are identified and compared with experimental IR measurements.

(Online publication February 21 2012)

Key Words:

  • energetic material;
  • polymerization;
  • infrared (IR) spectroscopy