Skip to main content

Structure and Reactivity of Ices, Amorphous Solids, and Supercooled Liquid Solutions at Interfaces and in the Condensed Phase


EMSL Project ID
39898

Abstract

The objective of this research is to examine physiochemical phenomena occurring at the surface and within the bulk of ices, amorphous solids, and supercooled liquid solutions. Our approach will be to use molecular beams to synthesize 'chemically tailored' nanoscale films as model systems to study ices, amorphous materials, and supercooled liquids. In addition to their utility as a synthetic tool, molecular beams are ideally suited for investigating the heterogeneous chemical properties of these novel films. Modulated molecular beam techniques enable us to determine the adsorption, diffusion, sequestration, reaction, and desorption kinetics in real-time. The dynamics and kinetic processes occurring in the nanoscale films are probed using variety of experimental techniques including temperature programmed desorption (TPD), atomic beam surface scattering, Auger, LEED, XPS, and FTIR spectroscopies. Elucidation of these processes will further our understanding of solvation and reactions in multi-phase, multi-component solutions and in determining reaction mechanisms in heterogeneous systems. Studying the properties of the supercooled liquid just above the glass transition temperature (Tg) is important for the understanding of this phenomenon. In particular, understanding the physics related to the formation of an amorphous solid, or glass, from its supercooled liquid is difficult because of their inherent metastability towards crystallization at temperatures approaching the glass transition temperature (Tg). Amorphous solid water (ASW) is of special importance for many reasons, including the open question over its applicability as a model for liquid water, and fundamental interest in the properties of glassy materials. In addition to the properties of ASW itself, understanding the intermolecular interactions between ASW and an adsorbate is important in such diverse areas as solvation in aqueous solutions, cryobiology, atmospheric, and environmental chemistry.

Project Details

Project type
Large-Scale EMSL Research
Start Date
2010-10-01
End Date
2013-09-30
Status
Closed

Team

Principal Investigator

R. Smith
Institution
Pacific Northwest National Laboratory

Team Members

Yuntao Xu
Institution
Pacific Northwest National Laboratory

Collin Dibble
Institution
Pacific Northwest National Laboratory

Robert May
Institution
Pacific Northwest National Laboratory

Jake Knox
Institution
Pacific Northwest National Laboratory

Jesper Matthiesen
Institution
Pacific Northwest National Laboratory

Zdenek Dohnalek
Institution
Pacific Northwest National Laboratory

Bruce Kay
Institution
Pacific Northwest National Laboratory

Tsun-Mei Chang
Institution
University of Wisconsin, Parkside

Related Publications

Ayotte P, P Marchand, JL Daschbach, RS Smith, and BD Kay. 2011. "HCI Adsorption and Ionization on Amorphous and Crystalline H2O Films below 50 K." Journal of Physical Chemistry A 115(23):6002-6014.
J. Matthiesen, R. S. Smith, and B. D. Kay, “Measuring diffusivity in supercooled liquid nanoscale films using inert gas permeation. II. Diffusion of Ar, Kr, Xe, and CH4 through Methanol”, Journal of Chemical Physics 133, 174505 (2010).
J. Matthiesen, R. S. Smith, and B. D. Kay, “Mixing It Up: Measuring Diffusion in Supercooled Liquid Solutions of Methanol and Ethanol at Temperatures near the Glass Transition”, Journal of Physical Chemistry Letters 2, 557 (2011).
May RA, RS Smith, and BD Kay. 2011. "Probing the Interaction of Amorphous Solid Water on a Hydrophobic Surface: Dewetting and Crystallization Kinetics of ASW on Carbon Tetrachloride." Physical Chemistry Chemical Physics. PCCP 13(44):19848-19855. doi:10.1039/C1CP21855G
May RA, RS Smith, and BD Kay. 2012. "The Molecular Volcano Revisited: Determination of Crack Propagation and Distribution During the Crystallization of Nanoscale Amorphous Solid Water Films. ." The Journal of Physical Chemistry Letters 3(3):327-331. doi:10.1021/jz201648g
P. Ayotte, P. Marchand, J. Daschbach, R. S. Smith, and B. Kay, “HCl Adsorption and Ionization on Amorphous and Crystalline H2O Films below 50 K”, Journal of Physical Chemistry A, DOI: 10.1021/jp110398j (2011).
R. S. Smith, J. Matthiesen, and B. D. Kay, “Measuring diffusivity in supercooled liquid nanoscale films using inert gas permeation. I. Kinetic model and scaling methods”, Journal of Chemical Physics 133, 174504 (2010).
R. S. Smith, J. Matthiesen, J. Knox, and B. D. Kay, “Crystallization Kinetics and Excess Free Energy of H2O and D2O Nanoscale Films of Amorphous Solid Water”, Journal of Physical Chemistry A, dx.doi.org/10.1021/jp110297q (2011).
Smith RS, and BD Kay. 2012. "Breaking Through the Glass Ceiling: Recent Experimental Approaches to Probe the Properties of Supercooled Liquids near the Glass Transition." The Journal of Physical Chemistry Letters 3(6):725-730. doi:10.1021/jz201710z
Smith RS, J Matthiesen, JR Knox, and BD Kay. 2011. "Crystallization Kinetics and Excess Free Energy of H2O and D2O Nanoscale Films of Amorphous Solid Water." Journal of Physical Chemistry A 115(23):5908-5917. doi:10.1021/jp110297q
Smith RS, NG Petrik, GA Kimmel, and BD Kay. 2012. "Thermal and Non-thermal Physiochemical Processes in Nanoscale Films of Amorphous Solid Water." Accounts of Chemical Research 45(1):33-42. doi:10.1021/ar200070w