From Sticky-Hard-Sphere to Lennard-Jones-Type Clusters

TL;DR

This paper establishes a relationship between sticky hard sphere clusters and Lennard-Jones potential minima, revealing how cluster stability and structure depend on potential parameters and size, with implications for modeling molecular clusters.

Contribution

It introduces a mapping between SHS clusters and Lennard-Jones minima, analyzing how cluster structures vary with potential parameters and size, and compares different Lennard-Jones potentials.

Findings

Number of stable clusters increases exponentially with size for N > 10.

Most missing Lennard-Jones structures are energetically unfavorable.

Extended Lennard-Jones potentials significantly increase cluster diversity.

Abstract

A relation $\mathcal{M}_{\mathrm{SHS}\to\mathrm{LJ}}$ between the set of non-isomorphic sticky hard sphere clusters $\mathcal{M}_\mathrm{SHS}$ and the sets of local energy minima $\mathcal{M}_{LJ}$ of the $(m,n)$-Lennard-Jones potential $V^\mathrm{LJ}_{mn}(r) = \frac{\varepsilon}{n-m} [ m r^{-n} - n r^{-m} ]$ is established. The number of nonisomorphic stable clusters depends strongly and nontrivially on both $m$ and $n$, and increases exponentially with increasing cluster size $N$ for $N \gtrsim 10$. While the map from $\mathcal{M}_\mathrm{SHS}\to \mathcal{M}_{\mathrm{SHS}\to\mathrm{LJ}}$ is non-injective and non-surjective, the number of Lennard-Jones structures missing from the map is relatively small for cluster sizes up to $N=13$, and most of the missing structures correspond to energetically unfavourable minima even for fairly low $(m,n)$. Furthermore, even the softest Lennard-Jones potential predicts that the coordination of 13 spheres around a central sphere is problematic (the Gregory-Newton problem). A more realistic extended Lennard-Jones potential chosen from coupled-cluster calculations for a rare gas dimer leads to a substantial increase in the number of nonisomorphic clusters, even though the potential curve is very similar to a (6,12)-Lennard-Jones potential.