Luminescence spectroscopy of atomic zinc in rare-gas solids I

Bracken, Veronica A.; McCaffrey, John G.; Gürtler, Peter

doi:10.1063/1.474239

Journal Article

PUBDB-2017-07479

Luminescence spectroscopy of atomic zinc in rare-gas solids I

Bracken, V. A. ; Gürtler, P.Extern* ; McCaffrey, J. G. (Corresponding author)

1997
American Institute of Physics Melville, NY

The journal of chemical physics 107(14), 5290 - 5299 (1997) [10.1063/1.474239]

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Please use a persistent id in citations: doi:10.1063/1.474239

Abstract: Steady-state and time-resolved luminescence spectroscopy of atomic zinc isolated in thin film samples of the solid rare gases, prepared by the cocondensation of zinc vapor with argon, krypton, and xenon has been recorded at 6.3 K using synchrotron radiation. Pairs of emission bands result from photoexcitation of the singlet 4p 1P1←4s 1S04p 1P1←4s 1S0 resonance transition of atomic zinc, even in annealed samples. In Zn/Ar the pair of emission bands were observed in the uv at 218.9 and 238 nm and for Zn/Xe in the near-uv at 356 and 399 nm. For the Zn/Kr system two emission bands were observed in the uv region at 239.5 and 259 nm but in addition, a weaker band was present in the near-uv at 315.6 nm. In a given annealed rare-gas host, the excitation profiles recorded for all the emission bands are identical, exhibiting the threefold splitting characteristic of Jahn-Teller coupling in the triply degenerate excited 1P11P1 state. These excitation profiles are identified as the solid phase equivalent of the 4p 1P1←4s 1S04p 1P1←4s 1S0 resonance transition of atomic zinc occurring at 213.9 nm in the gas phase. Based on their spectral positions and temporal decay characteristics, the emission bands observed in the uv and near-uv spectral regions have been assigned as the singlet and triplet transitions, respectively, of atomic zinc. The origin of the pairs of emission bands is ascribed to the Jahn-Teller coupling between noncubic vibronic modes of the lattice and the excited 4p4p orbital of the 1P11P1 state of atomic zinc, resulting in the coexistence of two energy minima. In Zn/Ar, the effects of slow vibrational relaxation in the excited singlet state were evident in the relative intensities and temporal decay profiles of the pair of emission bands. Specifically, the lower energy emission band was favored with excitation of the highest energy component of the threefold split Jahn-Teller absorption band, while the higher-energy emission was favored with excitation of the lowest-energy component. The intensity of the triplet state emission was observed to be enhanced in the heavier rare gases, being completely absent in Ar, weak in Kr, and the only emission observed in Xe.

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