ABSTRACT
The x-ray absorption spectrum of N_{2}^{+} in the K-edge region has been measured by irradiation of ions stored in a cryogenic radio frequency ion trap with synchrotron radiation. We interpret the experimental results with the help of restricted active space multiconfiguration theory. Spectroscopic constants of the 1σ_{u}^{-1} ^{2}Σ_{u}^{+} state, and the two 1σ_{u}^{-1}3σ_{g}^{-1}1π_{g} ^{2}Π_{u} states are determined from the measurements. The charge of the ground state together with spin coupling involving several open shells give rise to double excitations and configuration mixing, and a complete breakdown of the orbital picture for higher lying core-excited states.
ABSTRACT
The size dependent electronic structure and separate spin and orbital magnetic moments of free Co[Formula: see text] ([Formula: see text]) cluster ions have been investigated by x-ray absorption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap. A very large orbital magnetic moment of [Formula: see text] per atom was determined for Co[Formula: see text], which is one order of magnitude larger than in the bulk metal. Large orbital magnetic moments per atom of ≈1 [Formula: see text] were also found for Co[Formula: see text], Co[Formula: see text], and Co[Formula: see text]. The orbital contribution to the total magnetic moment shows a non-monotonic cluster size dependence: The orbital contribution increases from a local minimum at n = 2 to a local maximum at n = 5 and then decreases with increasing cluster size. The 3d spin magnetic moment per atom is nearly constant and is solely defined by the number of 3d holes which shows that the 3d majority spin states are fully occupied, that is, 3d hole spin polarization is 100%.
ABSTRACT
The Φ9/24 ground state of the Ni2+ 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±0.2 K was reached by buffer gas cooling of the molecular ion. The contribution of the spin dipole operator to the x-ray magnetic circular dichroism spin sum rule amounts to 7Tz=0.17±0.06µB 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.
ABSTRACT
The electronic structure and magnetic moments of free Mn2 (+) and Mn3 (+) are characterized by 2p x-ray absorption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap that is coupled to a synchrotron radiation beamline. Our results directly show that localized magnetic moments of 5 µB are created by 3d(5)((6)S) states at each ionic core, which are coupled ferromagnetically to form molecular high-spin states via indirect exchange that is mediated in both cases by a delocalized valence electron in a singly occupied 4s derived antibonding molecular orbital with an unpaired spin. This leads to total magnetic moments of 11 µB for Mn2 (+) and 16 µB for Mn3 (+), with no contribution of orbital angular momentum.
ABSTRACT
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, charge transfer multiplet calculation, and density functional theory study of size-selected free chromium-doped gold clusters. The observed size dependence of the local magnetic moment can be understood as a transition from a local moment to a mixed valence regime. This shows that the Anderson impurity model essentially describes finite systems even though the discrete density of states introduces a significant deviation from a bulk metal, and the free electron gas is only formed by less than 10 electrons. Electronic shell closure in the gold host minimizes the interaction of localized impurity states with the confined free electron gas and preserves the magnetic moment of 5 µ_{B} fully in CrAu_{2}^{+} and almost fully in CrAu_{6}^{+}. 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 stabilizes the local magnetic moment of the impurity atom.
ABSTRACT
The (6)Π electronic ground state of the Co2 (+) diatomic molecular cation has been assigned experimentally by x-ray absorption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap. Three candidates, (6)Φ, (8)Φ, and (8)Γ, for the electronic ground state of Fe2 (+) have been identified. These states carry sizable orbital angular momenta that disagree with theoretical predictions from multireference configuration interaction and density functional theory. Our results show that the ground states of neutral and cationic diatomic molecules of 3d transition elements cannot generally be assumed to be connected by a one-electron process.
ABSTRACT
Magnetic spin and orbital moments of size-selected free iron cluster ions Fe{n}{+} (n=3-20) have been determined via x-ray magnetic circular dichroism spectroscopy. Iron atoms within the clusters exhibit ferromagnetic coupling except for Fe{13}{+}, where the central atom is coupled antiferromagnetically to the atoms in the surrounding shell. Even in very small clusters, the orbital magnetic moment is strongly quenched and reduced to 5%-25% of its atomic value while the spin magnetic moment remains at 60%-90%. This demonstrates that the formation of bonds quenches orbital angular momenta in homonuclear iron clusters already for coordination numbers much smaller than those of the bulk.
ABSTRACT
A method to determine band gaps of size-selected and isolated nanoparticles by combination of valence band and core-level photoionization spectroscopy is presented. This approach is widely applicable and provides a convenient alternative to current standard techniques for the determination of band gaps by optical or photoelectron spectroscopy. A first application to vanadium doped silicon clusters confirms a striking size-dependence of their highest occupied-lowest unoccupied molecular orbital gaps.
ABSTRACT
Resonant 2p x-ray absorption spectra of size-selected transition metal ions and clusters consisting of 1
