The absorption and excitation spectroscopy of matrix-isolated atomic manganese: sites of isolation in the solid rare gases.
This study collects information from absorption and luminescence excitation spectra recorded for Mn atoms isolated in the solid rare gases Ar, Kr, and Xe and presents an analysis of the site occupancy, based on the polarizabilities of the rare gases and the observed spectral shifts. Two thermally stable sites of isolation exist for atomic Mn in solid Ar and Kr, while a single thermally stable site is present in Mn/Xe. Site occupancy assignments are based on the application of a polarizability model to the z (6)P(5/2)<--a (6)S(5/2); z (8)P(5/2)<--a (6)S(5/2), and y (6)P(5/2)<--a (6)S(5/2) electronic transitions of atomic Mn. From an analysis of the observed RG matrix-to-gas phase energy shifts for P<--S type transitions, this model allows the association of certain site types occupied by metal atoms in the rare gas solids. The required condition being a linear dependence of the matrix shifts with rare gas polarizability for those metal atoms "trapped" in a particular site type. Application of the polarizability model in conjunction with trends observed in site dominance, established a connection between the blue sites in Ar and Kr and the single site in Xe. Use of the known MgRG ground state bond lengths facilitated an identification of the sites of Mn atom isolation assuming the transference of the known MgRG bond lengths to the MnRG systems. Substitutional site occupancy of atomic Mn is assigned to the blue sites in Ar and Kr and the single site in Xe, while tetra-vacancy site occupancy is assigned to the red sites in Ar and Kr. Consistent with these assignments, Mn atoms in solid Ar show a preference for trapping in tetra-vacancy sites whereas in solid Kr, single substitutional sites are preferred and in Xe, this is the only site observed.
Collier
Martin A
MA
Department of Chemistry, National University of Ireland-Maynooth, Maynooth, County Kildare, Ireland.
McCaffrey
John G
JG