Finite-size effects and the stabilized spin-polarized jellium model for metal clusters

Abstract

In the framework of spherical geometry for jellium and local spin density approximation, we have obtained the equilibrium $r_s$ values, $\bar{r}_s(N,\zeta)$, of neutral and singly ionized "generic" $N$-electron clusters for their various spin polarizations, $\zeta$. Our results reveal that $\bar{r}_s(N,\zeta)$ as a function of $\zeta$ behaves differently depending on whether $N$ corresponds to a closed-shell or an open-shell cluster. That is, for a closed-shell one, $\bar{r}_s(N,\zeta)$ is an increasing function of $\zeta$ over the whole range $0\le\zeta\le 1$, and for an open-shell one, it has a decreasing part corresponding to the range $0<\zeta\le\zeta_0$, where $\zeta_0$ is a polarization that the cluster assumes in a configuration consistent with Hund's first rule. In the context of the stabilized spin-polarized jellium model, our calculations based on these equilibrium $r_s$ values, $\bar{r}_s(N,\zeta)$, show that instead of the maximum spin compensation (MSC) rule, Hund's first rule governs the minimum-energy configuration. We therefore conclude that the increasing behavior of the equilibrium $r_s$ values over the whole range of $\zeta$ is a necessary condition for obtaining the MSC rule for the minimum-energy configuration; and the only way to end up with an increasing behavior over the whole range of $\zeta$ is to break the spherical geometry of the jellium background. This is the reason why the results based on simple jellium with spheroidal or ellipsoidal geometries show up MSC rule.