Carbon vacancy-assisted stabilization of individual Cu₅ clusters on graphene. Insights from ab initio molecular dynamics

Abstract

Recent advances in synthesis and characterization methods have enabled the controllable fabrication of atomically precise metal clusters (AMCs) of subnanometer size that possess unique physical and chemical properties, yet to...

High‐level ab initio evidence of bipyramidal Cu5 clusters as fluxional Jahn‐Teller molecules

“…The same values between braces were reported in Ref. [55] but using density fitting. CuÀ Cu distances (in Å) between selected nearest neighbours atoms in the optimized Cu5 structures are presented (see Figure 2).…”

“…A good performance has been achieved with this scheme in describing both supported and unsupported subnanometer-sized silver [23,67] and copper [15,68] clusters, including different isomers of the Cu 5 cluster and the (Cu 5 ) 2 dimer. [54,55] In this work, the application of the DFTÀ D3 ansatz to the Jahn-Teller distorted potential energy surfaces of Cu 3 and Cu 5 clusters is a much more stringent test of its performance. Preliminary geometry optimizations with the RMP2 and DFTÀ D3 methods were carried out using density fitting but without imposing symmetry constraints.…”

“…[9,29,48,[51][52][53] On the computational side, a recent study has applied multi-reference ab initio theory to investigate whether pentamer Cu 5 clusters can couple to each other in such a way that their initial structures and charge distributions can be preserved. [3,54] Further evidence on the dimerization of supported Cu 5 clusters has been delivered from ab initio molecular dynamics, [55] considering defect-free graphene as the support. Interestingly, using multi-reference ab initio methods, both transition [54] and energy minimum [51,55] configurations have been identified for bipyramidal Cu 5 clusters in the doublet spin state, already indicating the possible existence of a Jahn-Teller distortion.…”

“…[3,54] Further evidence on the dimerization of supported Cu 5 clusters has been delivered from ab initio molecular dynamics, [55] considering defect-free graphene as the support. Interestingly, using multi-reference ab initio methods, both transition [54] and energy minimum [51,55] configurations have been identified for bipyramidal Cu 5 clusters in the doublet spin state, already indicating the possible existence of a Jahn-Teller distortion. In order to assess it, we apply multireference Rayleigh Schrödinger (second-order) per-turbation theory [56] (denoted RS2C) and the single-reference 'gold standard' coupled cluster singles and doubles and perturbative triples [CCSD(T)] method, proving convergence with large electronic basis sets.…”

Exploring Metal Nanocluster Catalysts for Ammonia Synthesis Using Informatics Methods: A Concerted Effort of Bayesian Optimization, Swarm Intelligence, and First-Principles Computation

“…The Sc 8 cluster, optimized using the PSO algorithm, has an adjacent bicapped octahedron structure; the Cu 5 cluster has a planar trapezoidal two-dimensional structure. The most stable structures of these metal clusters have been reported in previous studies. − The structures of these clusters that we have identified using PSO are in perfect agreement with those reported in the previous studies. Ideally, one would like to compare the computationally determined structures with experimental results, as has been done in recent studies, , but a comparison with the structures presented in the literature provides some evidence that the PSO algorithm is good at accurately searching for stable structures.…”