# Comment on “Density functional theory study of some structural and energetic properties of small lithium clusters” [J. Chem. Phys. 105, 9933 (1996)]

The experimentally determined size-evolutionary patterns (SEPs) of simple metal clusters pertaining to ionization potentials (IPs), electron affinities, and monomer separation energies have attracted much attention in the past ten years , since they may reflect the electronic shell structure of clusters (the major features of SEPs are associated with steps at magic numbers, but often there is in addition substantial fine structure, such as odd-even alternations).

Due to the required computational effort, first-principles (FP) theoretical studies (which incorporate the ionic geometry) of such SEPs are usually limited to cluster sizes of the order of ten atoms.  Recently, however, systematic theoretical investigations of such SEPs have been performed for a broad range of cluster sizes using the jellium-related Shell-Correction-Method (SCM) approach. 

In a recent article, Gardet et al.  have studied the IPs of small lithium clusters Li<sub>N</sub> (with $`N12`$) using a FP - density functional theory (DFT) and found reasonable agreement between theory and experiment. Furthermore, through a comparison of their results with those obtained from Kohn-Sham local-density-approximation (KS-LDA) calculations on a spherical jellium background,  they concluded that the jellium model is inadequate for a proper description of the IPs of such systems.

The purpose of this comment is to clarify that, while modelling the ions in a cluster via a uniform jellium background is certainly an approximation, the above conclusion of Gardet et al. pertains to limitations introduced through neglect of deviations from spherical symmetry, rather than to the jellium approximation itself. Indeed, in a series of papers,  we have demonstrated that consideration of triaxial shape deformations drastically improves the agreement between the jellium approximation and experiment for all instances of the aforementioned SEPs and for sizes up to 100 atoms, as well as for a variety of metal species (namely, alkali metals, such and Na and K, and noble metals, such as Cu and Ag).

To further elucidate the importance of shape deformations, we display in Fig. 1 the IPs of small Li<sub>N</sub> clusters (in the same size-range as with Ref. ) calculated  with our SCM for three different families of shapes of the jellium background \[namely, spherical, spheroidal (axially symmetric), and ellipsoidal (triaxial)\], and compare them to the experimental measurements. 

Fig. 1 reveals that spherical shapes (top panel) exhibit a characteristic sawtoothed profile, well known from previous spherical KS-LDA studies  and similar to the curve  labeled jellium-LDA in Fig. 12 of Ref. . Apart from major-shell closures, this sawtoothed profile describes the data rather poorly (notice in particular the absence of fine structure between major shell closures at $`N=2`$, 8 and 20).

The spheroidal model (middle panel) exhibits substantial improvement in describing the experimental trend. Furthermore, the ellipsoidal case (bottom panel) improves the agreement between the SCM results and experiment even further, in particular in the size range $`11N14`$. The essential improvement introduced by the deformations over the spherical case concerns the very good description of the subshell closure at $`N=14`$ and of odd-even alternations between major shell closures.

In summary, we have illustrated once again that, within the jellium approximation, deformed cluster shapes provide an adequate description of the observed systematic size dependence of the properties of simple metal clusters and should necessarily be employed in comparisons with other theoretical approaches.

This research is supported by the US Department of Energy (Grant No. FG05-86ER-45234). Studies were performed at the Georgia Institute of Technology Center for Computational Materials Science.