Abstract
The interactions of two model dipolar molecules (acetonitrile (ACN) and methanol (MeOH)) with amorphous solid water (ASW) were investigated using temperature-programmed desorption and temperature-dependent secondary ion mass spectrometry of a series of mixed adlayer thin film systems comprising different configurations of monolayers and thin films of ACN, MeOH, and ASW as well as a nonpolar probe molecule, CO2, deposited on a Ni(111) substrate. The temperature-dependent desorption rates and surface compositions of these systems were found to be consistent with the hydrophobic hydration of ACN, wherein the ACN is caged by water molecules, likely in clathrate-like structures. Consequently, the ACN–water hydrogen bonds are limited to the interior surfaces of the cages. The ACN is not incorporated into the ASW hydrogen bonding network, and it does not modify the crystallization kinetics of the ASW. In contrast, MeOH incorporates into the hydrogen bonding network and modifies the water crystallization kinetics...
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