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The DFT calculations within the DMol3 code used the generalized gradient approximation with the spin-restricted PW91 functional. The Kohn-Sham one-electron equations were solved on a basic set of double numerical plus d functions (comparable to a Gaussian 6-31G(d, with kinetic energies below 5.0 Å, and semi-core pseudo-potentials described the ionic cores. The Pt(111) surface was modeled by a four-layer slab, separated by an 11 Å thick vacuum. H adsorptions on a bare Pt(111) and the H pre-adsorbed Pt(111) were included in a 2′1 super-cell. In all cases, H and the first two Pt layers were allowed to relax, while the Pt atoms in the bottom two layers were fixed at the substrate's lattice position. The differential adsorption energy of H on Pt(111) was expressed as ΔEH, E[(i, 1)H/Pt(111, 1/2E(H2, E[iH/Pt111, where i is the number of H atoms pre-adsorbed per unit cell. In addition, for each optimized structure, a Mulliken
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