PF3, PF2, and PF on Ni(111): Theoretical aspects of their chemisorption

Abstract
The chemisorption of PF3, PF2, and PF on Ni(111) is examined, using tight binding extended Hückel calculations on a three‐layer model slab. We have studied various adsorption sites. Calculations indicate that PF3 should be preferentially bound to the onefold on‐top Ni sites, with P–F bonds azimuthally oriented over neighboring Ni atoms. PF2 is indicated to bind in a ‘‘perpendicular’’ manner at a twofold bridging site or possibly at a threefold site; and PF to the threefold hollow sites. These calculations are in agreement with experimental findings. PF3 remains a σ donor and a π acceptor (through backbonding) on the surface; in the bonding of PF2 and PF the π interaction is more important.

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