Charge trapping and transport over
chemical defects in
polyethylene
have significant impacts on its electrical and dielectric properties.
However, the dynamics of this phenomenon and its underlying mechanisms
remain unclear. To understand this fundamental aspect, we conducted
a time-domain ab initio nonadiabatic molecular dynamics study of phonon-assisted
holes dynamics in polyethylene over CO and C–OH defect
states. Our results suggest that the hole transfer and energy fluctuations
substantially depend on temperature and local morphology. When the
temperature decreases from 300 to 100 K, the hole transfer efficiency
and the energy fluctuations are severely suppressed due to the weakened
interactions between holes and phonons. Furthermore, amorphous polyethylene
exhibits a severe suppression of the hole transfer process compared
to crystalline polyethylene. An explanation for the influence of morphology
on the hole transfer process can be found in the differences in the
hole–phonon coupling and the electronic coupling between two
chemical defect states in crystalline and amorphous polyethylene.
Advancing the fundamental understanding of the dynamics of hole transfer
over chemical effects in polymers is a key to improving their insulating
properties for the next-generation high-voltage cables.