Work Function Change on Monolayer Adsorption

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Abstract
A self-consistent treatment is presented of the change in work function, or surface potential, produced by the adsorption of an immobile or mobile regular array of adsorbate entities on a plane (usually conducting) adsorbing surface. The adsorbed entities may be polarizable atoms, ions, or molecules, and the molecules and ions may have orientable permanent dipole moments, not assumed fixed in direction. The depolarizing field at a given adsorbed element arising from the total polarization of all its surrounding elements is taken into account in all cases, as is the possible presence of an average charge on the adsorbing surface. A distinction is introduced between the ``natural'' field polarizing a single adsorbate entity and the similar effective field leading to some time-average permanent dipole polarization. General formulas for surface potential in terms of surface charge and surface coverage are derived for all cases and compared with earlier, less general treatments of the same cases. The results are applied to electrolyte double-layer measurements and surface-potential determinations.

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