Resonance Raman and electronic absorption spectra of O−3 ions in γ-irradiated KClO3 and NaClO3

Abstract

Resonance Raman and electronic absorption spectra have been measured for the ozonide ion, O−3, produced in single crystals of KClO3 and NaClO3 by irradiation with γ rays. The O−3 ions are oriented in four to six symmetrically nonequivalent positions in KClO3 and appear to be oriented in two nonequivalent positions in NaClO3. Differences between the nonequivalent orientations affect both the ground and excited electronic states of O−3 as well as its ground vibrational states. The progressions of ν1 observed in the electronic spectra show that the vibrational spacing of ν1 in the excited electronic state is about 857 cm−1 as compared with the ground state spacing of about 1020 cm−1. Measurements of relative Raman intensities obtained with different exciting lines indicates that excitation near the center of a vibronic transition (0–n′) produces extra enhancement of the intensity of the nν1 vibrational transition.

The electron-spin magnetic moments (g factors) of O3−, O3Li, and O3Na: An ab initio study

“…The vertical ⌬E predicted for 1 2 A 2 of O 3 Ϫ ͑2.724 eV͒ agrees very well with an experimental maximum near 2.75 eV, 15 as well as with prior ab initio results ͑footnote b in Table XII͒.…”

“…15 The small magnetic coupling between X 2 B 1 and 1 2 A 2 (1a 2 →2b 1 ) is understandable since both 2b 1 and 1a 2 are MOs, resulting in small values of both L and SO upon a rotation along the x axis. Also, the spin-density distributions are quite different, with 2b 1 mainly localized on the central O atom but 1a 2 only having contributions of both terminal atoms.…”

Optische Absorptions-Spektroskopie an ionischen Ozoniden

“…In Anlehnung hieran wurde die an Einkristallen der ionischen Ozonide KO 3 , RbO 3 , und N(CH 3 bei relativ hohen Temperaturen angedeutet [25]. In festen Matrizes isoliertes O 3 ± zeigt eine mit den Spektren in Lo È sung vergleichbare Lage des Absorptionsmaximums und ebenfalls eine klar aufgelo È ste vibronische Feinstruktur [8,12,13]. Auch in Lo È sung findet sich kein Hinweis auf einen weiteren Ûbergang bei kleiner Energie.…”

On the intensity of electronic and vibrational resonant Raman scattering

“…This parameter x represents alternatively a measure of the effective strength of the coupling between the electron and the vibrational mode, The general case of wb # wo has been considered before (Elliott and Miranda 1975 Hence, depending upon the effective electron-phonon coupling (i.e., the value of x) the resonant vibrational Raman intensity may either present a maximum with respect to v at v -x (strong coupling, x + 1) or exhibit a normal behaviour, namely, always decreasing (weak coupling, x A A). This is apparently the case for 0; centres in yirradiated alkali chlorate and nitrates (Bates andPigg 1975, Gualberto et ul 1976) as shown in figure 1. The two components of the vibrational Raman intensity are associated with the two non-equivalent positions that the 0; ions can occupy in the lattice.…”

“…Experimentally, however, while there are few experimental determinations of absolute Raman intensities (Macfarlane and Ushioda 1970), relative measurements show that the single phonon lines are usually stronger than the electronic ones. Furthermore, recent resonant Raman measurements on 0; centres in y-irradiated chlorates and nitrates (Bates andPigg 1975, Gualberto et a1 1977) show an unusual behaviour of the relative vibrational line intensities. In such systems the vibrational Raman intensity is split into two components which are associated with the two non-equivalent positions that the 0; ions can occupy in the lattice.…”