Gold–Hydrogen Analogy in Small–Sized Hydrogen–Doped Gold Clusters Revisited

Abstract

The analogy between gold and hydrogen is a subject of long‐standing debate. In the present work, we examine the validity of the gold‐hydrogen analogy in a series of small‐sized H‐doped gold clusters, Aun−1H with n varying between 2 and 10 and also investigate its dependence on the cluster size. Keeping in mind the importance of the role of structures, we make use of the genetic algorithm coupled with a density functional theory based method to exhaustively search and identify the energetically low‐lying structures of each of the H‐doped gold clusters. These lower energy structures of H‐doped and pristine gold clusters are then employed to carry out the calculations of their electronic properties, stability analysis as well as their reactivity towards the adsorption and activation of CO and O2 molecules. Our study shows that in line with the gold‐hydrogen analogy, both electronic properties and the adsorption/activation characteristics of H‐doped gold clusters remain very similar to those of pristine gold clusters.

Hydride Locations and Planar σ‐Aromaticity in Hydrido‐Coinage‐Metal Clusters

“…In order to more clearly compare the effect of H atoms doping on the clusters, the structure characteristics of bare M clusters can be referred to the previous reports. Most of Au n H structures in our results are consistent with those reported by Megha at n=2–5, 7, 8, but different isomers are derived at n=6 and 9 [44] . Here we only give optimized structures of M n H (M=Cu, Ag and Au; n =2–9) clusters.…”

“…Most of Au n H structures in our results are consistent with those reported by Megha at n = 2-5, 7, 8, but different isomers are derived at n = 6 and 9. [44] Here we only give optimized structures of M n H (M=Cu, Ag and Au; n = 2-9) clusters. For M 2 H, both the Cu 2 H and Au 2 H have tilted structures, while the Ag 2 H has a linear geometry where the H atom is inserted to two Ag atoms.…”

Bonding and Electronic Interactions of Hydrogen with Gold Superatoms

“…Therefore, the H atom provides its 1s electron as a valence electron and behaves like a surrogate of the Au atom. Theoretical calculation by Ghanty and Banerjee demonstrated that the geometric and electronic structures of HAu n –1 ( n = 2–10, 20) are similar to those of pristine Au n . , Figure compares the geometric structures of the most stable isomers of Au n and HAu n –1 ( n = 2–10, 20). Both Au n and HAu n –1 ( n = 2–10) possess planar structures except HAu 9 .…”

“…Most stable structures of Au n and HAu n –1 ( n = 2–10, and 20). Color code: yellow = Au; cyan = H. Reproduced with permission from refs and . Copyright 2016 American Chemical Society and Copyright 2022 Wiley-VCH GmbH.…”

“…Comparison of (a) E b , (b) E CO , and (c) E O2 for Au n (black line) and HAu n –1 (red line). The data was extracted and replotted from ref . Copyright 2022 Wiley-VCH GmbH.…”