SIMULATION OF ATOMIC ZINC LUMINESCENCE IN RARE-GAS SOLIDS - A LOCALIZED PAIR POTENTIALS APPROACH

The luminescence spectroscopy of atomic zinc isolated in the solid rar e gases (Zn/RG) is compared with theoretical predictions obtained from the sum of diatomic Zn.RG and RG.RG pair potentials. In particular th e existence of pairs of emission bands, both of which are assigned to the same gas phase electronic transition, is examined with the use of diatomic pair potentials to simulate the potential energy surfaces of the Jahn-Teller active vibrational modes of Zn in the solid rare gases Ar, Kr, and Xe. Simulations of the solid state Zn/RG luminescence are developed from a consideration of the excited state Zn(P-1(1)).RG(n) van der Waals cluster species in the gas phase. The maximum binding en ergy of the Zn(P-1(1)).RG(n) clusters is found in the Zn.RG(4) cluster having a square planar structure at the energy minimum. Based on the results of the cluster calculations, lattice distortions which led to a dominant interaction between the Zn atom and four of its host atoms were sought to simulate the solid state luminescence. Two such vibroni c modes were identified; one a lattice mode in which four rare gas ato ms contract on a single plane toward the Zn atom, referred to as the w aist mode, and the other a motion of the Zn atom toward an octahedral interstitial site of the lattice, the body mode. Energy calculations o f these modes were carried out for rigid and relaxed rare gas lattices allowing identification of the high energy emission bands in the Zn/R G systems as arising from the waist mode, while the lower energy bands are associated with the body mode. The model also rationalizes the di fferences exhibited in the time-resolved behavior of the pairs of sing let emission bands in the Zn/Ar and Zn/Kr systems, whereby the lower e nergy band of a given system shows a risetime of a few hundred picosec onds while the higher energy band exhibits direct feeding. The steep g radient calculated on the waist mode, feeding the high energy band, an d the flat gradient found on the body mode, feeding the lower energy e mission, are consistent with the existence of a risetime in the latter and its absence in the former;. The close agreement found between the ory and experiment indicates the validity of using pair potentials in analysis of matrix zinc spectroscopy and thereby indicates that the lu minescence is controlled by localized guest-host interactions. (C) 199 7 American Institute of Physics.