Charge transfer transitions of the O2+–Ar and O2+–N2 complexes.

Autor: Catani, Katherine J., Bartlett, Nastasia I., Scholz, Michael S., Muller, Giel, Taylor, Peter R., Bieske, Evan J.
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Zdroj: Journal of Chemical Physics; 7/14/2023, Vol. 159 Issue 2, p1-10, 10p
Abstrakt: Electronic transitions are observed for the O 2 + –Ar and O 2 + –N2 complexes over the 225–350 nm range. The transitions are not associated with recognized electronic band systems of the respective atomic and diatomic constituents (Ar+, Ar, O 2 + , O2, N 2 + , and N2) but rather are due to charge transfer transitions. Onsets of the O 2 + –Ar and O 2 + –N2 band systems occur at 3.68 and 3.62 eV, respectively, corresponding to the difference in the ionization potentials of Ar and O2 (3.69 eV), and N2 and of O2 (3.51 eV), suggesting the band systems arise from intramolecular charge transfer transitions to states correlating with O2 (X 3 Σ g − ) + Ar+ (2Pu) and O2 (X 3 Σ g − ) + N 2 + (X 2 Σ g + ) limits, respectively. The dominant vibronic progressions have ωe values of 1565 cm−1 for O 2 + –Ar and 1532 cm−1 for O 2 + –N2, reasonably close to the value for the neutral O2 molecule in its X 3 Σ g − state (1580 cm−1). Higher energy band systems for O 2 + –Ar and O 2 + –N2 are assigned to transitions to states correlating with the O2 (a1Δg) + Ar+ (2Pu) and O2 (a1Δg) + N 2 + (X 2 Σ g + ) limits, respectively. [ABSTRACT FROM AUTHOR]
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