4.5 Article

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

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JOURNAL OF PHYSICAL CHEMISTRY B
卷 110, 期 1, 页码 507-511

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AMER CHEMICAL SOC
DOI: 10.1021/jp0555955

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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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