Low energy structures of gold nanoclusters in the size range 3–38 atoms

Abstract

Using a combination of first principles calculations and empirical potentials we have undertaken a systematic study of the low energy structures of gold nanoclusters containing from 3 to 38 atoms. A Lennard-Jones and many-body potential have been used in the empirical calculations, while the first principles calculations employ an atomic orbital, density functional technique. For the smaller clusters (n = 3, 4 and 5) the potential energy surface has been mapped at the ab initio level, for larger clusters an empirical potential was first used to identify low energy candidates which were then optimised with full ab initio calculations. At the DFT-LDA level, planar structures persist up to 6 atoms and are considerably more stable than the cage structures by more than 0.1 eV/atom. The difference in ab initio energy between the most stable planar and cage structures for 7 atoms is only 0.04 eV/atom. For larger clusters there are generally a number of minima in the potential energy surface lying very close in energy. Furthermore our calculations do not predict ordered structures for the magic numbers n = 13 and 38. They do predict the ordered tetrahedral structure for n = 20. The results of the calculations show that gold nanoclusters in this size range are mainly disordered and will likely exist in a range of structures at room temperature.

Theoretical insights into the structural, relative stable, electronic, and gas sensing properties of PbnAun (n = 2–12) clusters: a DFT study

“…In order to uncover the structural, energetic and electronic properties of Au n (n ¼ 3-14) clusters, Li et al 19 carried out systematical calculations by density functional theory, the results show that those Au n clusters with even numbers of atoms are more stable than their neighboring clusters, and the two-dimensional to three-dimensional transition occurs at n ¼ 12. De Bas et al 25 employed a combination of empirical potentials and rst principles method to further explore the low energy structures of the large Au n (n ¼ 3-38) nanoclusters. It is found that the Au n clusters are disordered and could be stable at room temperature.…”

Not so loosely bound rare gas atoms: finite-temperature vibrational fingerprints of neutral gold-cluster complexes

“…Such well-defined species represent an ideal situation for modeling and analyzing their properties by means of experiments and ab initio calculations. In the past years, the structure of small gold clusters has been studied in a series of works at various levels of theory [5][6][7][8][9][10]. Combined theoretical and experimental works on anions [11][12][13][14][15] and cations [14,16] yielded a consistent picture of the charged-cluster structures at all small sizes and, in particular, were able to identify the size at which three-dimensional (3D) structures become more stable than two-dimensional (2D) isomers.…”

Modelling water adsorption on Au(210) surfaces. I. A force field for water–Au interactions by DFT

“…The structure of the metallic surface has been considered in some water-metal interaction models, based on quantum mechanical calculations involving clusters of various metals like platinum [12,16,30,33] and copper [20,34], with different low-index crystallographic orientations. As electronic correlation effects are considerable, DFT methods are commonly used [32,[35][36][37][38].…”