Different dynamic behaviors of the dissociation and recombination reactions in a model calculation of polyethylene by first-principles steered molecular dynamics simulation

作者：Higuchi Yuji; Ishikawa Takeshi; Ozawa Nobuki; Chazeau Laurent; Cavaille Jean Yves; Kubo Momoji^*

来源：Chemical Physics, 2015, 459: 96-101.

DOI：10.1016/j.chemphys.2015.08.007

• First-principles molecular dynamics simulation
• Polyethylene
• Degradation

We investigate the different dynamics of the stress-induced dissociation and recombination reactions in a model of polyethylene by a first-principles molecular dynamics simulation at the B3LYP/6-31g(d) level. The dissociation under external forces acting on the chemical reaction site at 300 K follows the same pathway as the one calculated by the static first-principles method because it has a similar activation barrier to that of the static first-principles calculation. On the other hand, in the recombination process, thermal fluctuations causes collisions between hydrogen atoms at the chain ends. Furthermore, when external forces do not directly act on the chemical reaction site, two different dissociation processes are observed. On the other hand, recombination process is not observed due to rarely contact of the radical carbon. These results indicate that dissociation and recombination dynamics are very different, showing the importance of the dynamic calculation.

• 出版日期2015-9-28