Structural Influence on Superatomic Orbitals of Typical Gold Nanostructure Building Blocks

Abstract

We compared superatomic orbitals mainly contributed by 6s atomic orbitals among spherical core–shell cluster Au13, hexagonal plane Au7 and a (5,5) nanotube segment Au35 through first-principles density functional theory calculations. The compatibility between geometry and orbital morphology influences both the presence and the energy level order of particular superatomic orbitals. Taking Au13 as a reference, which possesses a regular configuration of 1S21P61D5, the hexagonal Au7 in 1S21P41D1 lacks the 1P occupied superatomic orbital which is distributed out of the structural plane. Different from the nearly degenerated five occupied 1D orbitals in Au13, Au35 in 1S21P61D101F101G61H1 shows energy separations over 4.0 eV between split 1D regions and 1F regions according to the preference of tubular geometry to different orbital morphologies. The structural reliance of the electronic structure revealed by these typical building blocks might be informative for bottom-up design and fabrication of nanoscale devices based on a gold nanostructure and contributes to the variety and operability of nanoscale materials.