Theoretical analysis of magnetic coupling in sandwich clusters V_n(C_6H_6)_{n+1}

TL;DR

This paper investigates the stability of ferromagnetism in V_n(C_6H_6)_{n+1} sandwich clusters through first-principles calculations and models, revealing the roles of different V-benzene bonds and their impact on magnetic coupling.

Contribution

It provides a detailed analysis of the bonding mechanisms and their influence on ferromagnetism in sandwich clusters, with a new model incorporating edge benzene effects.

Findings

V 3d_z^2 orbital forms a weak sigma-bond, contributing little to magnetic coupling.

In-plane d_x^2-y^2 and d_xy orbitals hybridize with benzene LUMO, crucial for magnetic interactions.

Edge benzene modifies ferromagnetism stability, explained by a constructed physical model.

Abstract

The mechanism of ferromagnetism stability in sandwich clusters V$_n$(C$_6$H$_6$)$_{n+1}$ has been studied by first-principles calculation and model analysis. It is found that each of the three types of bonds between V and benzene (Bz) plays different roles. V 3d$_{z^2}$ orbital, extending along the molecular axis, is weakly hybridized with Bz's HOMO-1 orbital to form the $\sigma$-bond. It is quite localized and singly occupied, which contributes 1$\mu_B$ to the magnetic moment but little to the magnetic coupling of neighboring V magnetic moments. The in-plane d$_{x^2-y^2}$, d$_{xy}$ orbitals are hybridized with the LUMO of Bz and constitute the $\delta$-bond. This hybridization is medium and crucial to the magnetic coupling though the $\delta$ states have no net contribution to the total magnetic moment. d$_{xz}$, d$_{yz}$ and HOMO of Bz form a quite strong $\pi$-bond to hold the molecular structure but they are inactive in magnetism because their energy levels are far away from the Fermi level. Based on the results of first-principles calculation, we point out that the ferromagnetism stability is closely related with the mechanism proposed by Kanamori and Terakura [J. Kanamori and K. Terakura, J. Phys. Soc. Jpn. 70, 1433 (2001)]. However, the presence of edge Bz's in the cluster introduces an important modification. A simple model is constructed to explain the essence of the physical picture.