Luminescence of atomic magnesium in inert low temperature solids. I. Argon and krypton

Abstract

Absorption and luminescence spectra have been recorded in the 200–700 nm range for atomic magnesium isolated in solid Ar and Kr at 12 K. Strong absorptions occurring in the near UV at 285 nm, showing a threefold splitting, are identified as the solid phase equivalent of the gas phase 3p 1P1←3s 1S0 Mg atom transition. Evidence of multiple site trapping of Mg atoms in Ar and Kr matrices formed at 12 K has been obtained from annealing studies in absorption, but especially in luminescence spectroscopy. The single emission band of Mg/Ar, centered at 297.6 nm, exhibits a radiative lifetime of 1.12 ns and is thereby assigned as singlet 3p 1P1→3s 1S0 Mg atom fluorescence. The luminescence exhibited by the Mg/Kr system is more complex than the Mg/Ar system in that a weak visible band at 472 nm occurs as well as several bands in the UV having nanosecond lifetimes. The richness of the Mg/Kr UV spectra has been examined with annealing and time-resolved measurements and identified as arising from multiple trapping site effects, with at least three spectrally distinct sites identified. Efficient resonant radiative energy transfer is demonstrated to be occurring between two of these sites and an average separation between the sensitizor and activator sites is calculated to be 60 nm at a Mg:Ar dilution ratio of 3:104. Annealing of Mg/Kr samples to 45 K was found to remove all but one site which exhibits emission at 297.6 nm and a very weak band at 472.6 nm. The former, having a radiative lifetime of 1.25 ns, is assigned as 3p 1P1→3s 1S0 Mg atom fluorescence; the latter with a radiative lifetime of 8.9 ms, is assigned as 3p 3P1→3s 1S0 Mg atom phosphorescence.