title: Breaking through the glass ceiling: the correlation between the self-diffusivity in and krypton permeation through deeply supercooled liquid nanoscale methanol films.
abstract: Molecular beam techniques, temperature-programmed desorption (TPD), and reflection absorption infrared spectroscopy (RAIRS) are used to explore the relationship between krypton permeation through and the self-diffusivity of supercooled liquid methanol at temperatures (100-115 K) near the glass transition temperature, T(g) (103 K). Layered films, consisting of CH(3)OH and CD(3)OH, are deposited on top of a monolayer of Kr on a graphene covered Pt(111) substrate at 25 K. Concurrent Kr TPD and RAIRS spectra are acquired during the heating of the composite film to temperatures above T(g). The CO vibrational stretch is sensitive to the local molecular environment and is used to determine the supercooled liquid diffusivity from the intermixing of the isotopic layers. We find that the Kr permeation and the diffusivity of the supercooled liquid are directly and quantitatively correlated. These results validate the rare-gas permeation technique as a tool for probing the diffusivity of supercooled liquids.
authors.affiliation: Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, P.O. Box 999, Mail Stop K8-88, Richland, Washington 99352, USA. scott.smith@pnl.gov
authors.forename: R Scott
authors.initials: RS
authors.lastname: Smith
authors.forename: Jesper
authors.initials: J
authors.lastname: Matthiesen
authors.forename: Bruce D
authors.initials: BD
authors.lastname: Kay