Raman scattering from the peroxide ion in Cs₂O₂

Abstract

The Raman spectrum of Cs 2 O 2 excited at 632.8 nm shows a single O 2 −2 fundamental band at wavenumber of 742.5 cm −1 and second and third overtones at 1468.5 and 2176.8 cm −1 , respectively. The harmonic wavenumber ! e = 759.5 ± 0.7 cm −1 and anharmonicity constant ! e x e = 8.4 ± 0.3 cm −1 were calculated directly from the measurements. These results are compared with ! e = 1151.0 ± 1.5 cm −1 and ! e x e = 9.6 ± 0.5 cm −1 recently found for O 2 − ion in CsO 2 by others. The lower ! e x e of O 2 −2 relative to that of O 2 − indicates a broader (smaller curvature) anharmonic oscillator potential well.

Accommodation of Excess Oxygen in Group II Monoxides

“…The values given in Table III are similar to other data concerning the wavenumber of peroxide ions in Cs 2 O 2 (742.5 cm À1 ) 24 and H 2 O 2 (880 cm À1 ). 25 This gives some confidence in the predicted values.…”

Evaluating chemical bonding in dioxides for the development of metal–oxygen batteries: vibrational spectroscopic trends of dioxygenyls, dioxygen, superoxides and peroxides

“…Small, light cations have concentrated charge with stronger electrostatic forces of attraction and may even be able to abstract O 2 À electron density producing a covalent-like interaction, whilst the reverse is true for ions where the charge is dispersed over a large mass and area. (Table 3) as observed by Livneh et al 9 Due to their high \ C iv values; Cs + (4678 g mol À1 Å 3 C À1 ) and TBA + (78 656 g mol À1 Å 3 C À1 ) are weak coordinating cations. Colour-coordinated axis labels are shown above the graph.…”

A high-rate and high-efficiency molten-salt sodium–oxygen battery

“…3a). For instance, the Raman bands at 737 and 792 cm À1 are consistent with those reported for the A 0 1 and A 0 2 vibration modes of Na 2 O 2 , 44 while those at 756 and 781 cm À1 can be attributed to O-O stretching of Cs 2 O 2 (A g mode) 45 and K 2 O 2 (A g mode), 44…”