Optical absorption of matrix isolated Li, Na, and Ag clusters and microcrystals

Abstract

Optical absorption spectra are reported for Li, Na, and Ag in various stages of aggregation ranging from atom to microcrystal. The samples were prepared by the simultaneous condensation of rare gas and metal vapor onto a liquid helium temperature substrate. The dependence of the strength of the individual absorption lines on metal concentration and on selective light induced diffusion allowed the tentative assignment of spectral features to one, two, three, and four atom clusters. Comparison of the observed transition energies with an empirical, extended Hückel calculation seems to indicate that the trimers are triangular and the four atom clusters have tetrahedral shape. For metal concentrations higher than 10% the sharp molecular lines abruptly disappear and a single broad plasmon absorption, characteristic of microcrystals, appears. The shape of this absorption band can be explained using a continuum theory of dielectric response if microcrystal size, shape, and mutual interaction are properly taken into account.