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Interactions of Polyelectrolytes with Water and Ions at Air/Water Interfaces Studied by Phase-Sensitive Sum Frequency Generation Vibrational Spectroscopy

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Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1Z1, Canada
*E-mail: [email protected] (K.C.C.).
Cite this: J. Phys. Chem. C 2013, 117, 30, 15698–15703
Publication Date (Web):July 3, 2013
Copyright © 2013 American Chemical Society

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    Interactions of the polyelectrolyte partially hydrolyzed polyacrylamide (HPAM) with water and cations at air/liquid interfaces were studied using phase-sensitive sum frequency generation (SFG) vibrational spectroscopy. In contrast to the conventional SFG vibrational spectroscopy which measures only the amplitude of the second-order susceptibility |χ(2)|, the heterodyne-detected SFG measures the complex χ(2) which contains information about the absolute orientation of surface molecules. While the OH groups of water near a neat air/water interface mostly pointed down to the bulk (downward), the presence of the polyelectrolyte caused flipping of water molecules with the hydrogen being oriented upward. With 10–7 M HPAM, water showed a highly ordered structure with a single peak near 3100 cm–1, but higher concentrations resulted in a less ordered water structure with multiple peaks. The addition of the monovalent cation Na+ to the polyelectrolyte solution did not affect the conformation of the polyelectrolyte, though the water molecules flipped back to a structure similar to that of a neat air/water interface with the hydrogen pointing down. On the other hand, the addition of divalent cation Ca2+ not only changed the conformation of the polyelectrolyte but also completely destroyed the ordered structure of interfacial water molecules. The observed phenomena support the polymer–ion complex model in which a divalent cation can interact with two intrachain or interchain charges and form a jointing point. The amorphous nature of the polymer–ion complex explained the disappearance of the ordered water structure in the presence of divalent cations.

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