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A Reduction in Particle Size Generally Causes Body-Centered-Cubic Metals to Expand but Face-Centered-Cubic Metals to Contract

Nafday, Dhani and Sarkar, Subhrangsu and Ayyub, Pushan and Saha-Dasgupta, Tanusri (2018) A Reduction in Particle Size Generally Causes Body-Centered-Cubic Metals to Expand but Face-Centered-Cubic Metals to Contract. In: ACS NANO, 12 (7). pp. 7246-7252.

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Official URL: http://dx.doi.org/10.1021/acsnano.8b03360

Abstract

From a careful analysis of existing data as well as new measurements, we show that the size dependence of the lattice parameters in metal nanoparticles with face-centered cubic (fcc) and body-centered cubic (bcc) symmetries display opposite trends: nanoparticles with fcc structure generally contract with decreasing particle size, while those with bcc structure expand. We present a microscopic explanation for this apparently puzzling behavior based on first-principles simulations. Our results, obtained from a comparison of density functional theory calculations with experimental data, indicate that the nanoparticles are capped by a surface monolayer of oxygen atoms, which is routinely detected by surface-sensitive techniques. The bcc- and fcc-based nanoparticles respond in contrasting fashion to the presence of the oxygen capping layer, and this dictates whether the corresponding lattice parameter would increase or decrease with size reduction. The metal oxygen bonds at the surface, being shorter and stronger than typical metal metal bonds, pull the surface metal atoms outward. This outward movement of surface atoms influences the core regions to a larger extent in the relatively open bcc geometry, producing a rather large overall expansion of the cluster, compared to the bulk. In case of fcc clusters, on the other hand, the outward movement of surface metal atoms does not percolate too far inside, resulting in either a smaller net expansion or contraction of the cluster depending on the extent of surface oxygen coverage. Our study therefore provides a convincing physicochemical basis for the correlation between the underlying geometry and the nature of change of the lattice parameters under size reduction.

Item Type: Journal Article
Additional Information: Copy right for this article belong to AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Department/Centre: Division of Physical & Mathematical Sciences > Physics
Depositing User: Id for Latest eprints
Date Deposited: 23 Aug 2018 15:59
Last Modified: 23 Aug 2018 15:59
URI: http://eprints.iisc.ac.in/id/eprint/60488

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