Formation
and Infrared Spectroscopic Characterization
of Three Oxygen-Rich BiO<sub>4</sub> Isomers in Solid Argon
- Publication date
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Abstract
The
reactions of bismuth atoms and O<sub>2</sub> have been investigated
using matrix isolation infrared spectroscopy and density functional
theory calculations. The ground state bismuth atoms react with dioxygen
to form the BiOO and Bi(O<sub>2</sub>)<sub>2</sub> complexes spontaneously
on annealing. The BiOO molecule is characterized to be an end-on bonded
superoxide complex, while the Bi(O<sub>2</sub>)<sub>2</sub> molecule
is characterized to be a superoxo bismuth peroxide complex, [Bi<sup>3+</sup>(O<sub>2</sub><sup>–</sup>)(O<sub>2</sub><sup>2‑</sup>)]. Under UV–visible light irradiation, the Bi(O<sub>2</sub>)<sub>2</sub> complex rearranges to the more stable OBiOOO isomer,
an end-on bonded bismuth monoxide-ozonide complex. The end-on-bonded
OBiOOO complex further rearranges to a more stable side-on bonded
OBiO<sub>3</sub> isomer upon sample annealing. In addition, the bent
bismuth dioxide anion is also formed and assigned
