Excited state spectroscopy, subpicosecond predissociation, and solvation of diatomic XeO in solid rare gas hosts

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Abstract
Time, wavelength, and polarization resolved fluorescence techniques are used to investigate the photophysics of weakly bound diatomic XeO following frequency doubled dye laser excitation near 2200 Å. Photoselection experiments prove that the ’’Green bands’’ contain both E 1Σ→C 1ΣΠ and E 1Σ→B 1Σ fluorescences. The B 1Σ state, which correlates with O(1D)+Xe, is at least three vibrational quanta deeper than previously thought. An isotopic reversal of linewidths between Xe16O and Xe18O in the E 1Σ→B 1Σ spectra is interpreted in terms of subpicosecond homogeneous predissociation of B 1Σ. Solid phase homogeneous predissociation theory is discussed, and the isotopic sensitivity of the appropriate Franck–Condon factors is numerically investigated. The C 1Π and B 1Σ potentials are unambiguously deeper and more harmonic in solid Ar than in vacuum. This change in potential curve shape appears to reflect increased admixture of charge transfer (Xe+O−) components in the solid phase electronic wavefunctions.