Gas-phase anion complexes are produced containing one or more vanadium or titanium atoms bound to one or more molecules of the polycyclic aromatic hydrocarbon (PAH) coronene (C 24 H 12 ). These species are prepared with coincident laser vaporization of a metal rod and a pressed pellet of coronene in a pulsed-nozzle cluster source. The anion complexes produced are mass-selected with a time-of-flight spectrometer and photoexcited with various Nd:YAG laser harmonics. A magnetic bottle instrument is employed for time-of-flight photoelectron spectroscopy measurements on these complexes. Electron affinities (EA's) are observed to be greater for the organometallic complexes than they are for the isolated metal clusters or the isolated coronene molecule. EA's increase with the number of metal atoms in the complex. The spectra observed for V-coronene complexes are similar in appearance to those seen previously for V-benzene and V-C 60 , suggesting that the metal binds as a π complex in a symmetric ring site. V-(coronene) 2 complexes exhibit different spectra under different conditions attributed to the formation of sandwich and external-metal isomers.
Electronic spectra are reported for the heteronuclear metal dimers LiCu and LiAg, with resonant one-color two-photon ionization (R2PI). The dimers are produced in a pulsed supersonic molecular beam by laser vaporization of either a copper or silver rod coated with a thin film of vacuum deposited lithium metal. A total of twelve excited electronic states for LiCu and seven for LiAg are observed. Analysis of the vibrational progressions yields ground and excited state vibrational frequencies and dissociation energies for both LiCu and LiAg. In addition, selected vibronic bands are rotationally resolved. This data, together with that obtained by Morse and co-workers for LiCu [J. Chem. Phys. (to be published)], gives bond lengths for LiCu and LiAg (r0″=2.26 and 2.41 Å, respectively). The bond lengths for LiCu and LiAg are significantly shorter than expected by comparison to the homonuclear diatomics Li2 and Cu2 or Ag2. Dissociation energies in the heteronuclear dimers are also much greater than the mean of the corresponding homonuclear dimer values. These trends indicate that ionic character plays a leading role in the ground-state bonding.
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