HIGH VIBRATIONAL LEVELS OF $O_{2}(b^{1}\Sigma^{+}_{g})$ AND $O_{2}(a^{1}\Delta_{g})$

Relaxation of laser-excited $O_{2}(A^{3}\\Sigma^{+}_{u}$, $v = 6-10)$ in collisions with $O_{2}$ populates high vibrational levels of $O_{2}(b^{1}\\Sigma^{+}_{g})$ and $O_{2}(a^{1}\\Delta_{g})$. Previous work on the spectroscopy of $O_{2}$ emissions from the Earth's night atmosphere has enabled us to assign the Q-branches of thirteen $(v^{\\prime},v^{\\prime\\prime})$ bands in the $(2+1)$ REMPI spectra of $O_{2}(b^{1}\\Sigma^{+}_{g}$, $v^{\\prime\\prime}= 10 - 15)$ and $O_{2}(a^{1}\\Delta_{g}$, $v^{\\prime\\prime}= 16 - 19)$, through the intermediate Rydberg levels $3d\\pi {^{1}\\Sigma^{+}_{g}}(v^{\\prime} = 2 - 5)$ and $^{1}\\Delta = 4, 5)$, repectively. The derived spectroscopic constants for $O_{2}(b^{1}\\Sigma^{+}_{g}, v^{\\prime\\prime} = 10 - 13)$ agree with our previous work. Improved values are obtained for $v^{\\prime\\prime} = 14, 15$. Our constants for $3d\\pi {^{1}\\Sigma^{+}_{g}}(v^{\\prime\\prime}= 5)$ are the first available. Our spectra are better calibrated and our constants for the $v^{\\prime} = 2 - 4$ levels significantly more precise than the 1988-1992 work in the groups of Chupka and Houston. The energies of $O_{2}(a^{1}\\Delta_{g}, v^{\\prime\\prime} = 16 - 19)$ were known previously only to within about $80 cm^{-1}$ from the 1995 electron scattering work of Allan. The highest level known accurately from nightglow spectra is $v^{\\prime\\prime} = 11$. Our spectral analysis gives precise rotational constants and $\\Delta G$ values for these vibrational levels and for $3d\\pi {^{1}\\Delta_{g}} (v^{\\prime}= 4, 5)$. The absolute term energies are uncertain by about $5 cm^{-1}$ based on earlier work in the groups of Chupka and Houston. Supported by the NASA Geospace Sciences and Planetary Atmospheres programs and by the NSF Aeronomy and Physics/REU programs.