title: Local structure relaxation, quantum trap depression, and valence charge polarization induced by the shorter-and-stronger bonds between under-coordinated atoms in gold nanostructures.
abstract: Relativistic density functional theory calculations have been conducted to examine the effect of atomic under-coordination on the crystal structure, binding energy, and electron configuration of cuboctahedral and Marks decahedral gold clusters. Trend consistency between calculations and experimental observations confirmed the predictions made using BOLS correlation theory, suggesting that the shorter-and-stronger bonds between under-coordinated atoms induce local structure relaxation, potential well depression, and the associated local charge and energy densification, as well as the polarization of the otherwise conducting s-electrons (valence charge) by the densely- and tightly-trapped core electrons of which the binding energy shifts positively to deeper energies. Findings are in good agreement with scanning tunneling microscopy/spectroscopy results from monomers, dimers, chain ends, and nanostructures of gold and other metals.
authors.affiliation: School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798, Singapore.
authors.forename: Xi
authors.initials: X
authors.lastname: Zhang
authors.forename: Jer-lai
authors.initials: JL
authors.lastname: Kuo
authors.forename: Mingxia
authors.initials: M
authors.lastname: Gu
authors.forename: Xiaofeng
authors.initials: X
authors.lastname: Fan
authors.forename: Ping
authors.initials: P
authors.lastname: Bai
authors.forename: Qing-Gong
authors.initials: QG
authors.lastname: Song
authors.forename: Chang Q
authors.initials: CQ
authors.lastname: Sun
mesh_terms: D006046:Gold / Q000737:chemistry*; D053768:Metal Nanoparticles / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D006046:Gold