title: Investigation of finite-size effects in chemical bonding of AuPd nanoalloys.
abstract: In this paper, the size-dependent changes in energetic, vibrational, and electronic properties of C-O gas molecule interacting with surface Pd atom of a variety of AuPd nanoalloy structures are investigated by means of first principles calculations. The variation in C-O adsorption energies, C-O vibration frequencies (νC-O), and Pd d-bond centers (εd) on a series of non-supported Aun-1-Pd1 nanoparticles (with n varying from 13 to 147) and on two semi-finite surfaces are inspected with cluster size. We demonstrate for the first time that, with small AuPd bimetallic three-dimensional clusters as TOh38, one can reach cluster size convergence even for such a sensitive observable as the adsorption energy on a metal surface. Indeed, the results show that the adsorbate-induced perturbation is extremely local and it only concerns the isolated Pd interacting with the reactive gas molecule. Except for 13 atom clusters, in which molecular behaviour is predominant, no finite-size effects are observed for surface Pd atom substituted in AuPd free nanoclusters above 38 atoms.
authors.affiliation: Division of Interfacial Water and Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China.
authors.forename: Beien
authors.initials: B
authors.lastname: Zhu
authors.affiliation: CNRS-ICG UMR 5253, équipe MACS, 8 rue de l'Ecole Normale, 34296 Montpellier, France.
authors.forename: Ismail Can
authors.initials: IC
authors.lastname: Oğuz
authors.affiliation: CNRS-ICG UMR 5253, équipe MACS, 8 rue de l'Ecole Normale, 34296 Montpellier, France.
authors.forename: Hazar
authors.initials: H
authors.lastname: Guesmi