skip to main content

SciTech ConnectSciTech Connect

Title: Ionization and photofragmentation of Ru{sub 3}(CO){sub 12} and Os{sub 3}(CO){sub 12}

In this paper, we use a combination of photoelectron spectroscopy, mass spectrometry, and density functional theory calculations to get a detailed understanding of valence single and double ionization and the subsequent dissociation processes. This is exemplified on benchmark systems, trimetallo-dodecacarbonyls M{sub 3}(CO){sub 12} with M = Ru, Os, where the energy remaining in the molecule after photoionization can be retrieved by measuring the degree of fragmentation of the molecular ion. The intensity of different mass peaks can thus be directly related to ionization cross sections obtained by photoelectron spectroscopy. We find that the M—CO dissociation energy rises as the number of CO ligands decreases due to dissociation. Moreover, ionization of the CO ligands has a higher cross section than that of the metal center for both single and double ionization. After advanced fragmentation, a CO bond can break and the carbon atom remains bonded to the metal core. In addition, we found that the valence ionization cross sections of M{sub 3}(CO){sub 12} are maximal at about 40 eV photon energy thus showing a more pronounced shape resonance than Ru and Os-complexes with a single metal atom center. Finally, an np → nd giant resonance absorption causes a significant increase ofmore » the ionization cross section above 50 eV for Ru{sub 3}(CO){sub 12}.« less
Authors:
; ;  [1] ; ;  [2] ;  [3]
  1. Department of Chemical Physics, AlbaNova University Centre, Stockholm University, Roslagstullsbacken 21, SE-106 91 Stockholm (Sweden)
  2. Elettra-Sincrotrone Trieste, Area Science Park, I-34149 Basovizza, Trieste (Italy)
  3. Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala (Sweden)
Publication Date:
OSTI Identifier:
22493130
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 15; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; CARBON MONOXIDE; CROSS SECTIONS; DENSITY FUNCTIONAL METHOD; DISSOCIATION; DISSOCIATION ENERGY; EV RANGE; GIANT RESONANCE; MASS; MASS SPECTROSCOPY; METALS; MOLECULAR IONS; MOLECULES; OSMIUM COMPLEXES; PEAKS; PHOTOELECTRON SPECTROSCOPY; PHOTOIONIZATION; PHOTONS