Valence ionized states of iron pentacarbonyl and η5 -cyclopentadienyl cobalt dicarbonyl studied by symmetry-adapted cluster-configuration interaction calculation and collision-energy resolved Penning ionization electron spectroscopy

Ryoichi Fukuda, Masahiro Ehara, Hiroshi Nakatsuji, Naoki Kishimoto, Koichi Ohno

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)

Abstract

Valence ionized states of iron pentacarbonyl Fe (CO) 5 and η5 -cyclopentadienyl cobalt dicarbonyl Co (η5 -C5 H5) (CO) 2 have been studied by ultraviolet photoelectron spectroscopy, two-dimensional Penning ionization electron spectroscopy (2D-PIES), and symmetry-adapted cluster-configuration interaction calculations. Theory provided reliable assignments for the complex ionization spectra of these molecules, which have metal-carbonyl bonds. Theoretical ionization energies agreed well with experimental observations and the calculated wave functions could explain the relative intensities of PIES spectra. The collision-energy dependence of partial ionization cross sections (CEDPICS) was obtained by 2D-PIES. To interpret these CEDPICS, the interaction potentials between the molecules and a Li atom were examined in several coordinates by calculations. The relation between the slope of the CEDPICS and the electronic structure of the ionized states, such as molecular symmetry and the spatial distribution of ionizing orbitals, was analyzed. In Fe (CO) 5, an attractive interaction was obtained for the equatorial CO, while the interaction for the axial CO direction was repulsive. For Co (η5 -C5 H5) (CO) 2, the interaction potential in the direction of both Co-C-O and Co-Cp ring was attractive. These anisotropic interactions and ionizing orbital distributions consistently explain the relative slopes of the CEDPICS.

Original languageEnglish
Article number084302
JournalJournal of Chemical Physics
Volume132
Issue number8
DOIs
Publication statusPublished - 2010

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Valence ionized states of iron pentacarbonyl and η<sup>5</sup> -cyclopentadienyl cobalt dicarbonyl studied by symmetry-adapted cluster-configuration interaction calculation and collision-energy resolved Penning ionization electron spectroscopy'. Together they form a unique fingerprint.

Cite this