Enhanced Electronic g-Factors in Magic Number Main Group Bimetallic Nanoclusters

Abstract

We report the observation of large electronic g-factors in magic number main group bimetallic nanoclusters by performing Stern–Gerlach deflection experiments at 10 K. The clusters AlPb12 and InPb12 exhibit values of g = 3.5–4.0, whereas GaPb12 clusters surprisingly reveal a value of g < 2.0. Multireference ab initio methods are applied to unmask the origin of the g-factors and to gain insight into the electronic structure. The interplay of the pyritohedral molecular symmetry, a particularly strong spin–orbit coupling involved in the ground state, and the presence of low-lying degenerate excited states causes large positive g-factors in AlPb12 and InPb12. Contrarily, the spin–orbit coupling in the GaPb12 ground state is completely quenched. This is due to the d-block contraction lowering the nonbonding Ga 5s orbital and consequently forming an icosahedral ground state. Thus, endohedral p-doped tetrel clusters, composed of purely main group elements, state a novel and unique class of magnetic compounds and their study contributes to a more profound understanding of the metal–metal interaction in polynuclear clusters as well as magnetism at the molecular level.

Electrically controlled nonvolatile switching of single-atom magnetism in a Dy@C84 single-molecule transistor

“…By applying a linear fit to the level shift according to the Zeeman effect, it is possible to determine the effective g -factor 32 , 33 , which is defined as (where is the Bohr magneton). The absolute values of range from 2.2 to 8.4 (Table 1 ).…”

Magnetism of single-doped paramagnetic tin clusters studied using temperature-dependent Stern–Gerlach experiments with enhanced sensitivity: impact of the diamagnetic ligand field and paramagnetic dopant

“…42 By measuring the deflection at higher nozzle temperatures, the temperature-dependent magnetic response of the cluster can be interpreted using the Curie law with 16,43 Orbital contributions to the magnetic moment and thus deviations from pure spin magnetism are taken into account by introducing an effective spin quantum number S , which is why the g -factor then deviates from the value of the free electron. 41,44 Since the internal temperature T is not directly accessible from our experiments, T nozzle is used to analyse the magnetic deflection data. As will be shown, the assumption that T = T nozzle is valid for T nozzle > 90 K.…”

Adsorption of multiple NO molecules on Au10−and Au9Zn−planar clusters. A comparative DFT study

“…For future work, it will be interesting to consider the adsorption of other radicals, such as CO, as well as different dopants, such as Ga or Pb. Another perspective, raised by the high multiplicity of these Zn-doped compounds is the possibility of performing measurements of their magnetic g-factors, in line with the recent studies of Lehr and coworkers, 53,54 and references therein, on molecular magnetism.…”