Revisiting the potential-energy surface of CnBe3n+2H2n+22+ (n = 2–4) clusters: are planar pentacoordinate carbon structures the global minima?

Abstract

Using various exploration strategies, in this study, we investigated the potential energy surfaces (PES) of CBe₅H₅⁺ and C_nBe_3n+2H_2n+2²⁺ (n = 2–4) clusters. Previous studies proposed that the planar pentacoordinate carbons (ppCs) were the global minima of these clusters. However, our study identified new putative global minima and competitive isomers, refuting some previous assignments. We employed several methods, including evolutive-inspired stochastic approaches guided by “chemical criteria”, and ab initio molecular dynamics simulations at elevated temperatures. Our results showed that the size of the scanned population significantly affected the evolutive method and that constrained or guided procedures showed an advantage in identifying better minima for larger systems. This study demonstrated that using multiple complementary strategies can result in a wider variety of minima in a given energy range. Our findings provide valuable insights into exploring the potential energy surfaces of clusters, mainly medium-sized clusters, which could be the connections between small clusters and nanomaterials.