Breaking through the Glass Ceiling: The Correlation Between the Self-Diffusivity in and Krypton Permeation through Deeply Supercooled Liquid Nanoscale Methanol Films

Journal Article · Sun Mar 28 04:00:00 EDT 2010 · Journal of Chemical Physics, 132(12):Art. No. 124502

DOI:https://doi.org/10.1063/1.3361664· OSTI ID:978954

Smith, R Scott; Matthiesen, Jesper; Kay, Bruce D

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 near (100-115 K) the glass transition temperature, Tg (103 K). Layered films, consisting of CH3OH and CD3OH, are deposited ontop 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 Tg. 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.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 978954
• Report Number(s): PNNL-SA-69782; 24694; KC0301020
• Journal Information: Journal of Chemical Physics, 132(12):Art. No. 124502, Journal Name: Journal of Chemical Physics, 132(12):Art. No. 124502 Journal Issue: 12 Vol. 132; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

10 SYNTHETIC FUELS
ABSORPTION
DESORPTION
Environmental Molecular Sciences Laboratory
GLASS
HEATING
KRYPTON
METHANOL
MOLECULAR BEAMS
REFLECTION
SPECTRA
SPECTROSCOPY
SUBSTRATES
TRANSITION TEMPERATURE