Self-diffusion of supercooled o-terphenyl near the glass transition temperature

被引:199
|
作者
Mapes, MK [1 ]
Swallen, SF [1 ]
Ediger, MD [1 ]
机构
[1] Univ Wisconsin, Dept Chem, Madison, WI 53706 USA
关键词
D O I
10.1021/jp0555955
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
Self-diffusion coefficients for the low molecular weight glass former o-terphenyl have been measured near T-g by isothermally desorbing thin film bilayers of deuterio and protio o-terphenyl in a vacuum chamber. We observe translational diffusion that is about 100 times faster at T-g + 3 K than the Stokes-Einstein prediction. Predictions from random first order transition theory and a dynamic facilitation approach are in reasonable agreement with our results; in these approaches, enhanced translational diffusion is associated with spatially heterogeneous dynamics. Self-diffusion controls crystallization in o-terphenyl for most of the supercooled liquid regime, but at temperatures below T-g + 10 K, the reported crystallization rate increases suddenly while the self-diffusion coefficient does not. This work and previous work on trisnaphthylbenzene both find a self-diffusion-controlled crystal growth regime and an enhancement in self-diffusion near T-g, suggesting that these phenomena are general characteristics of fragile low molecular weight glass formers. We discuss the width of the relaxation time distributions of o-terphenyl and trisnaphthylbenzene as they relate to the observation of enhanced translational diffusion.
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页码:507 / 511
页数:5
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