Abstract
The atomic-scale structure of Zn 2+ incorporated at the CaCO 3 (10 1 ̄ 4) surface by adsorption from solution was determined by X-ray standing wave triangulation and surface extended X-ray absorption fine structure spectroscopy. At low coverage (approximately 0.1 ML), Zn 2+ substitutes for Ca 2+ in the surface layer. Structural relaxation of the adjacent in-plane CO 2− 3 ions in the host surface is shown by the reduced nearest-neighbor distance of Zn–O relative to Ca–O. Relaxation of the Zn 2+ ion in the out-of-plane direction is shown by the displacement of its lattice position from the ideal Ca 2+ position. These relaxations, resulting in a local lattice buckling feature at the Zn 2+ adsorption site, can be fully explained as the combined effect of the electrostatic relaxation of the nearest-neighbor anions in response to the smaller size of Zn 2+, and the bonding asymmetry due to surface truncation.
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