Synthesis of Hydrogen Polyoxides H₂O₄ and H₂O₃ and Their Characterization by Raman Spectroscopy

Abstract

Abstract Hydrogen tetroxide (H 2 O 4 ) and hydrogen trioxide (H 2 O 3 ) have been prepared in relatively large quantities as components of peroxy radical condensates. The polyoxides were characterized by the Raman spectra of the oxygen framework. Lines at 500, 756, and 878 cm –1 correspond to skeletal oscillations of H 2 O 3 in the condensate (OOO bend, asymmetric OO stretch, symmetric OO stretch). Lines at 449, 589, 624, 827, and 865 cm –1 match the skeletal vibrations of H 2 O 4 (OOO bend 1, OOO bend 2, center OO stretch, asymmetric OO stretch, symmetric OO stretch). The line of the O 4 torsion vibration of hydrogen tetroxide was not observed experimentally. The assignment was confirmed by B3LYP/6‐31+G(d,p) calculations of the vibrational spectra. According to the information available in the literature, this work is the only report of the preparation of H 2 O 4 in significant concentrations and its Raman spectrum. For the first time convincing evidence is provided for the existence of hydrogen tetroxide (in low‐temperature solids).