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

被引:1
作者
Higuchi, Yuji [1 ,2 ]
Ishikawa, Takeshi [3 ]
Ozawa, Nobuki [1 ]
Chazeau, Laurent [4 ]
Cavaille, Jean-Yves
Kubo, Momoji [1 ]
机构
[1] Tohoku Univ, IMR, Aoba Ku, Sendai, Miyagi 9808577, Japan
[2] PRESTO, JST, Saitama 3320012, Japan
[3] Tohoku Univ, Grad Sch Engn, FRRI, Aoba Ku, Sendai, Miyagi 9808579, Japan
[4] INSA Lyon, MATEIS, F-69621 Villeurbanne, France
关键词
First-principles molecular dynamics simulation; Polyethylene; Degradation; THERMAL-OXIDATION REACTIONS; LOW-DOSE RATE; HYDROPEROXIDE DECOMPOSITION; DENSITY POLYETHYLENE; ELECTRON-DENSITY; LOW-TEMPERATURE; POLYMERS; STATE; THERMOCHEMISTRY; REEXAMINATION;
D O I
10.1016/j.chemphys.2015.08.007
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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. (C) 2015 Elsevier B.V. All rights reserved.
引用
收藏
页码:96 / 101
页数:6
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