Electronic structure and reactivity of a biradical cluster: Sc3O6(-)

Phys Chem Chem Phys. 2011 Jun 7;13(21):10084-90. doi: 10.1039/c0cp02095h. Epub 2011 Apr 26.

Abstract

The Sc(3)O(6)(-) cluster anions were produced by laser ablation and studied by reaction with n-butane in a fast flow reactor and by photoelectron spectroscopy. The reactivity experiments indicated that one Sc(3)O(6)(-) cluster can activate two n-butane molecules consecutively with rate constants on the order of 10(-10) cm(3) molecule(-1) s(-1) under near room-temperature conditions, suggesting that the even-electron system Sc(3)O(6)(-) has a highly reactive electronic structure. The photoelectron spectroscopy determined a high vertical detachment energy (VDE) of 5.63 ± 0.08 eV for the Sc(3)O(6)(-) cluster. Density functional computations indicated that the lowest energy isomer of Sc(3)O(6)(-) is an oxygen-centered biradical with a high VDE and is highly reactive toward n-butane, which is in good agreement with the experiments. The Sc(3)O(6)(-) cluster may serve as an ideal model system to provide insight into the real-life chemistry involved with the coupled O(-)˙···O(-)˙ dimers over the surfaces of metal oxide catalysts.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anions / chemistry*
  • Butanes / chemistry*
  • Electrons
  • Models, Molecular
  • Photoelectron Spectroscopy
  • Quantum Theory
  • Scandium / chemistry*

Substances

  • Anions
  • Butanes
  • butane
  • scandium oxide
  • Scandium