Ground X 2Σ+ state potential well, and excited state dynamics of diatomic XeF in solid Ne and Ar

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Abstract
The ’’shape’’ of the ground state potential well of XeF in solid Ne has been obtained from an analysis of D (1/2) →X 2Σ+ resonance fluorescence. The constants ωe″=247 cm−1 and ωexe″=10.2 cm−1 give an extrapolated Morse oscillator De?1500 cm−1. The ground state well is only slightly deeper in the solid than in the gas phase (De?1160 cm−1). In solid Ar, the Te values for the excited D (1/2) and B (1/2) states undergo unprecedented red shifts of ?8% and ?13% respectively, apparently reflecting the charge transfer nature of these excited states. The extrapolated gas phase radiative lifetimes are τr=13±1 nsec for D (1/2), and τr=8±2 nsec for B (1/2). Polarized fluorescence studies prove that the gas phase 3500 Å lasing transition is B (1/2) →X 2Σ+. The influence of the Te red shift upon the excited state dynamics, and upon the X 2Σ+ well depth in the solid, is discussed. Unassigned emission spectra are also observed from other van der Waals complexes among Xe and F atoms.