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

Physical chemistry chemical physics : PCCP (2011-04-28)
Yan-Xia Zhao, Jin-Yun Yuan, Xun-Lei Ding, Sheng-Gui He, Wei-Jun Zheng
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.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Scandium(III) oxide, 99.9% trace rare earth metals basis
Sigma-Aldrich
Scandium(III) oxide, powder, 99.995% trace rare earth metals basis
Sigma-Aldrich
Scandium(III) oxide, 99.99% trace rare earth metals basis