How Many Isomers Do Metallic Clusters Have? Case of Magnesium Clusters of up to 55 Atoms

About 9000 structures of magnesium clusters Mg-n (n = 2-13) generated via different methods were optimized at the DFT levels in order to estimate the number of all possible stable structures that can exist for the given cluster size (similar to 820,000 PES points were explored in total). It was found that the number of possible cluster isomers N quickly grows with a number of atoms n; however, it is significantly lower than the number of possible nonisomorphic graph structures, which can be drawn for the given n. At the DFT potential energy surface, we found only 543 local minima corresponding to the isomers of Mg-2-Mg-13. The number of isomers obtained in the DFT optimizations grows with n approximately as n(4), whereas the N values extrapolated to the infinite generation process grow as n(8). The cluster geometries obtained from the global DFT optimization were then used to adjust two empirical potentials of Gupta type (GP) and modified Sutton-Chen type (SCG3) describing the interactions between the magnesium atoms. Using these potentials, the extensive sets of structures Mg,-Mg-55 (up to 30,000 clusters for each n) were optimized to obtain the dependence of the cluster isomer count on n in the continuous range of n = 2-30 and for selected n up to n = 55. It was found that the SCG3 potential, which is closer to the DFT results, gives a number of possible isomers growing as approximately n(8)(.9), whereas GP potential results in the n(4.3) dependence.

Automated summary

Optimized numerous magnesium cluster structures at the DFT level to estimate the number of possible isomers, which grow with the number of atoms but are significantly lower than the number of possible nonisomorphic graph structures. Adjusted two empirical potentials of Gupta type and modified Sutton-Chen type based on the DFT results, and optimized extensive sets of cluster structures to observe the influence of the potentials on the growth of possible isomers.