Photon energy dependence of the photoelectron spectra of the anthracene anion: On the influence of autodetaching states.

Vibrationally resolved photoelectron spectra of anthracene anions have been measured for photon energies between 1.13 and 4.96 eV. In this energy range, photoemission mostly occurs via autodetaching electronically excited states of the anion, which strongly modifies the vibrational excitation of the neutral molecule after electron emission. Based on the observed vibrational patterns, eight different excited states could be identified, seven of which are resonances known from absorption spectroscopy. Distinctly different photon energy dependencies of vibrational excitations have been obtained for different excited states, hinting at strongly different photoemission lifetimes. Unexpectedly, some resonances seem to exhibit bimodal distributions of emission lifetimes, possibly due to electronic relaxation processes induced by the excitation of specific vibrational modes.

X-Ray Absorption Spectrum of the N_{2}

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.

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.

Atomically precise (catalytic) particles synthesized by a novel cluster deposition instrument.

We report a new high vacuum instrument which is dedicated to the preparation of well-defined clusters supported on model and technologically relevant supports for catalytic and materials investigations. The instrument is based on deposition of size selected metallic cluster ions that are produced by a high flux magnetron cluster source. The throughput of the apparatus is maximized by collecting and focusing ions utilizing a conical octupole ion guide and a linear ion guide. The size selection is achieved by a quadrupole mass filter. The new design of the sample holder provides for the preparation of multiple samples on supports of various sizes and shapes in one session. After cluster deposition onto the support of interest, samples will be taken out of the chamber for a variety of testing and characterization.

Gas-phase calorimetry of protonated water clusters.

Protonated water clusters with 60 to 79 molecules have been studied by nanocalorimetry. The technique is based on multi-collision excitations of the accelerated clusters with helium. The caloric curves indicate transitions that resemble those of water clusters charged by an excess electron, but the transition temperatures of the protonated clusters are higher.

Communication: Highest occupied molecular orbital-lowest unoccupied molecular orbital gaps of doped silicon clusters from core level spectroscopy.

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.

Probing the angular momentum character of the valence orbitals of free sodium nanoclusters.

Although many properties of polyatomic metal clusters have been rationalized by an electron shell model resembling that used for free atoms, it remained unclear how reliable this analogy is with respect to the angular momentum eigenstate character of the electronic wave functions. We studied free size-selected negatively charged clusters of sodium atoms (Nan-) of approximately spherical shape (n = 19, 40, 55, 58, 147) by angle-resolved photoelectron spectroscopy over a broad range of photon energies (1.5 to 5 electron volts). Highly anisotropic, state- and energy-dependent angular distributions emerged for all sizes. Well-defined classes of energy dependence related to the approximate angular momenta of the bound-state orbitals indicate that the overall character of the valence electron wave functions is not appreciably influenced by the interaction with the ion background. The measured distributions nevertheless deviate strongly from the predictions of single-electron models, hinting at a distinct role of correlated multielectron effects in the photoemission process.

Observation of electron gas cooling in free sodium clusters.

Free size-selected Na+(n) (n = 16-250) clusters have been studied by femtosecond pump-probe photoelectron and photofragmentation spectroscopy. Thermal electron emission from the hot electron gas was used to monitor the energy transfer from the electronic system to lattice vibrations. The electron-phonon coupling constants determined for the different sizes can be described by the radius dependent function g(R) = (2.3 + 114 A2/R2) X 10(16) W/m3K. No strong quantum size effect was observed even for the smallest cluster size.

Caloric curve across the liquid-to-gas change for sodium clusters.

The caloric curve for Na(139)(+) has been measured from 100 K up to the temperature where the clusters are boiling hot and spontaneously emit atoms. In this limit the clusters form an evaporative ensemble, the temperature and energy of which have been determined. As the caloric curve of an atomic gas with a finite number of atoms is known, one can construct the caloric curve for this finite system below and above the boiling point. A conjecture is made on how to link the evaporative ensemble temperature of the free cluster in vacuum to the boiling temperature of a finite system at a given pressure. This allows one to determine the enthalpy of vaporization at the phase transition of the finite system.

Negative heat capacity for a cluster of 147 sodium atoms.

There exists a surprising theoretical prediction for a small system: its microcanonical heat capacity can become negative. An increase of energy can-under certain conditions-lead to a lower temperature. Here we present experimental evidence that a cluster containing exactly 147 sodium atoms does indeed have a negative microcanonical heat capacity near its solid to liquid transition.