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Register a new userSpectroscopy of PTCDA attached to rare gas samples: clusters vs. bulk matrices. I. Absorption spectroscopy
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The interaction between PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) and rare gas or para-hydrogen samples is studied by means of laser-induced fluorescence excitation spectroscopy. The comparison between spectra of PTCDA embedded in a neon matrix and spectra attached to large neon clusters shows that these large organic molecules reside on the surface of the clusters when doped by the pick-up technique. PTCDA molecules can adopt different conformations when attached to argon, neon and para-hydrogen clusters which implies that the surface of such clusters has a well-defined structure and has not liquid or fluxional properties. Moreover, a precise analysis of the doping process of these clusters reveals that the mobility of large molecules on the cluster surface is quenched, preventing agglomeration and complex formation.
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The interaction between PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) molecules and solid rare gas samples is studied by means of fluorescence emission spectroscopy. On the one hand, laser-excited PTCDA-doped large argon, neon and para-hydrogen clusters in comparison with PTCDA embedded in helium nanodroplets are spectroscopically characterized with respect to line broadening and shifting. A fast non-radiative relaxation is observed before a radiative decay in the electronic ground state takes place. On the other hand, fluorescence emission studies of PTCDA embedded in bulk neon and argon matrices results in much more complex spectral signatures characterized by a splitting of the different emission lines. These can be assigned to the appearance of site isomers of the surrounding matrix lattice structure.
Small lanthanide clusters have interesting magnetic properties, but their structures are unknown. We have identified the structures of small terbium cluster cations Tb (n = 5-9) in the gas phase, by analysis of their vibrational spectra. The spectra have been measured via IR multiple photon dissociation of their complexes with Ar atoms in the 50-250 1/cm range with an infrared free electron laser. Density functional theory calculations using a 4f-in-core effective core potential (ECP) accurately reproduce the experimental far-IR spectra. The ECP corresponds to a 4f85d16s2 trivalent configuration of terbium. The assigned structures are similar to those observed in several other transition metal systems. From this, we conclude that the bonding in Tb clusters is through the interactions between the 5d and 6s electrons, and that the 4f electrons have only an indirect effect on the cluster structures.
The rare-earths are known to have intriguing changes of the valence, depending on chemical surrounding or geometry. Here we make predictions from theory that combines density functional theory with atomic multiplet-theory, on the transition of valence when transferring from the atomic divalent limit to the trivalent bulk, passing through different sized clusters, of selected rare-earths. We predict that Tm clusters show an abrupt change from pure divalent to pure trivalent at a size of 6 atoms, while Sm and Tb clusters are respectively pure divalent and trivalent up to 8 atoms. Larger Sm clusters are argued to likely make a transition to a mixed valent, or trivalent, configuration. The valence of all rare-earth clusters, as a function of size, is predicted from interpolation of our calculated results. We argue that the here predicted behavior is best analyzed by spectroscopic measurements, and provide theoretical spectra, based on dynamical mean field theory, in the Hubbard-I approximation, to ease experimental analysis.
We present a combined experimental and theoretical study on the rotationally inelastic scattering of OH ($X,^2Pi_{3/2}, J=3/2, f$) radicals with the collision partners He, Ne, Ar, Kr, Xe, and D$_2$ as a function of the collision energy between $sim 70$ cm$^{-1}$ and 400~cm$^{-1}$. The OH radicals are state selected and velocity tuned prior to the collision using a Stark decelerator, and field-free parity-resolved state-to-state inelastic relative scattering cross sections are measured in a crossed molecular beam configuration. For all OH-rare gas atom systems excellent agreement is obtained with the cross sections predicted by close-coupling scattering calculations based on accurate emph{ab initio} potential energy surfaces. This series of experiments complements recent studies on the scattering of OH radicals with Xe [Gilijamse emph{et al.}, Science {bf 313}, 1617 (2006)], Ar [Scharfenberg emph{et al.}, Phys. Chem. Chem. Phys. {bf 12}, 10660 (2010)], He, and D$_2$ [Kirste emph{et al.}, Phys. Rev. A {bf 82}, 042717 (2010)]. A comparison of the relative scattering cross sections for this set of collision partners reveals interesting trends in the scattering behavior.
Helium tagging in action spectroscopy is an efficient method for measuring the absorption spectrum of complex molecular ions with minimal perturbations to the gas phase spectrum. We have used superfluid helium nanodroplets doped with corannulene to prepare cations of these molecules complexed with different numbers of He atoms. In total we identify 13 different absorption bands from corannulene cations between 5500 {AA} and 6000 {AA}. The He atoms cause a small, chemically induced redshift to the band positions of the corannulene ion. By studying this effect as a function of the number of solvating atoms we are able to identify the formation of solvation structures that are not visible in the mass spectrum. The solvation features detected with the action spectroscopy agree very well with the results of atomistic modeling based on path-integral molecular dynamics simulations. By additionally doping our He droplets with D$_2$, we produce protonated corannulene ions. The absorption spectrum of these ions differs significantly from the case of the radical cations as the numerous narrow bands are replaced by a broad absorption feature that spans nearly 2000 {AA} in width.
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