Large orbital magnetic moments of small, free cobalt cluster ions Co[Formula: see text] with n [Formula: see text].

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%.

Direct observation of high-spin states in manganese dimer and trimer cations by x-ray magnetic circular dichroism spectroscopy in an ion trap.

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.

Electronic ground states of Fe2(+) and Co2(+) as determined by x-ray absorption and x-ray magnetic circular dichroism spectroscopy.

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.

Polycyclic aromatic hydrocarbon-isomer fragmentation pathways: case study for pyrene and fluoranthene molecules and clusters.

We report on measurements of the ionization and fragmentation of polycyclic aromatic hydrocarbon (PAH) targets in Xe(20+) + C(16)H(10) and Xe(20+) + [C(16)H(10)](k) collisions and compare results for the two C(16)H(10) isomers: pyrene and fluoranthene. For both types of targets, i.e., for single PAH molecules isolated in vacuum or for isomerically pure clusters of one of the molecules, the resulting fragment spectra are surprisingly similar. However, we do observe weak but significant isomer effects. Although these are manifested in very different ways for the monomer and cluster targets, they both have at their roots small differences (<2.5 eV) between the total binding energies of neutral, and singly and multiply charged pyrene and fluoranthene monomers. The results will be discussed in view of the density functional theory calculations of ionization and dissociation energies for fluoranthene and pyrene. A simple classical over-the-barrier model is used to estimate cross sections for single- and multiple-electron transfer between PAHs and ions. Calculated single and multiple ionization energies, and the corresponding model PAH ionization cross sections, are given.

Ions colliding with cold polycyclic aromatic hydrocarbon clusters.

We report the first experimental study of ions interacting with clusters of polycyclic aromatic hydrocarbon (PAH) molecules. Collisions between 11.25 keV 3He+ or 360 keV 129Xe20+ and weakly bound clusters of one of the smallest PAH molecules, anthracene, show that C14H10 clusters have much higher tendencies to fragment in ion collisions than other weakly bound clusters. The ionization is dominated by peripheral collisions in which the clusters, very surprisingly, are more strongly heated by Xe20+ collisions than by He+ collisions. The appearance size is k=15 for [C 14H10](k)2+.