arXiv subjects
Publications and source records attributed to B. v. Issendorff.
This article is a collection of contributions from speakers at the 2025 DEAMN [Dynamics of Electrons in Atomic and Molecular Nanoclusters] workshop at the Majorana Centre in Erice. Not ordinary contributions to a conference proceeding, this gives a new and different perspective on the work done by the workshop participants.
The $^{4}Φ_{9/2}$ ground state of the Ni$_2^+$ diatomic molecular cation is determined experimentally from temperature and magnetic-field-dependent x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap, where an electronic and rotational temperature of $7.4 \pm 0.2$ K was reached by buffer gas cooling of the molecular ion. The contribution of the magnetic dipole term to the x-ray magnetic circular dichroism spin sum rule amounts to $7\, T_z = 0.17 \pm 0.06$ $μ_B$ per atom, approximately 11 % of the spin magnetic moment. We find that, in general, homonuclear diatomic molecular cations of $3d$ transition metals seem to adopt maximum spin magnetic moments in their electronic ground states.
Spin and orbital magnetic moments of cationic iron, cobalt, and nickel clusters have been determined from x-ray magnetic circular dichroism spectroscopy. In the size regime of $n = 10 - 15$ atoms, these clusters show strong ferromagnetism with maximized spin magnetic moments of 1~$μ_B$ per empty $3d$ state because of completely filled $3d$ majority spin bands. The only exception is $\mathrm{Fe}_{13}^+$ where an unusually low average spin magnetic moment of $0.73 \pm 0.12$~$μ_B$ per unoccupied $3d$ state is detected; an effect, which is neither observed for $\mathrm{Co}_{13}^+$ nor $\mathrm{Ni}_{13}^+$.\@ This distinct behavior can be linked to the existence and accessibility of antiferromagnetic, paramagnetic, or nonmagnetic phases in the respective bulk phase diagrams of iron, cobalt, and nickel. Compared to the experimental data, available density functional theory calculations generally seem to underestimate the spin magnetic moments significantly. In all clusters investigated, the orbital magnetic moment is quenched to $5 - 25$\,\% of the atomic value by the reduced symmetry of the crystal field. The magnetic anisotropy energy is well below 65 $μ$eV per atom.
The magnetic moment of a single impurity atom in a finite free electron gas is studied in a combined x-ray magnetic circular dichroism spectroscopy and density functional theory study of size-selected free chromium-doped gold clusters. The observed size-dependence of the local magnetic moment can essentially be understood in terms of the Anderson impurity model. Electronic shell closure in the host metal minimizes the interaction of localized impurity states with the confined free electron gas and preserves the full magnetic moment of $\unit[5]{μ_B}$ in $\mathrm{CrAu}_{2}^{+}$ and $\mathrm{CrAu}_{6}^{+}$ clusters. Even for open-shell species, large local moments are observed that scale with the energy gap of the gold cluster. This indicates that an energy gap in the free electron gas generally stabilizes the local magnetic moment of the impurity.
The interaction of a single manganese impurity with silicon is analyzed in a combined experimental and theoretical study of the electronic, magnetic, and structural properties of manganese-doped silicon clusters. The structural transition from exohedral to endohedral doping coincides with a quenching of high-spin states. For all geometric structures investigated, we find a similar dependence of the magnetic moment on the manganese coordination number and nearest neighbor distance. This observation can be generalized to manganese point defects in bulk silicon, whose magnetic moments fall within the observed magnetic-to-nonmagnetic transition, and which therefore react very sensitively to changes in the local geometry. The results indicate that high spin states in manganese-doped silicon could be stabilized by an appropriate lattice expansion.
High resolution photoelectron spectra of cold mass selected Cu_n-, Ag_n- and Au_n- with n =53-58 have been measured at a photon energy of 6.42 eV. The observed electron density of states is not the expected simple electron shell structure, but seems to be strongly influenced by electron-lattice interactions. Only Cu55- and Ag55- exhibit highly degenerate states. This is a direct consequence of their icosahedral symmetry, as is confirmed by density functional theory calculations. Neighboring sizes exhibit perturbed electronic structures, as they are formed by removal or addition of atoms to the icosahedron and therefore have lower symmetries. Gold clusters in the same size range show completely different spectra with almost no degeneracy, which indicates that they have structures of much lower symmetry. This behaviour is related to strong relativistic bonding effects in gold, as demonstrated by ab initio calculations for Au55-.