Theory of Alkali Induced Reconstruction of the Cu(100) Surface

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LEED experiments show that Li adsorbed at Cu(100) surfaces at room temperature induces a (2x1) missing row substrate reconstruction while adsorption at lower temperatures, T=180 K, results in an unreconstructed Cu(100)+c(2x2)--Li overlayer structure. Substrate reconstruction has not been observed for Na nor for K adsorption. In order to study the specific reconstruction behavior of the Li adsorbate ab initio DFT calculations have been performed on Cu(100)+Ad, Ad = Li, Na, K systems at coverages Thetaₐd=0.25-0.5 with and without reconstruction. The calculations show that the (2x1) MR reconstructed surface lies energetically above the ideal (1x1) surface by 0.2 eV per unit cell. However, alkali binding is stronger in the MR geometry as compared to that of the ideal surface where the increase in bond strength becomes smaller in going from Li to Na to K. As a result, the MR reconstructed and the overlayer adsorbate systems are energetically very close for Cu(100)+Li while for Na and K the overlayer geometry is always favored.