The electronic spectra of the mixed mercury dihalides. Part 1. Computational procedures for calculating spectra, for a new route to equilibrium and formation constants, and the resolved spectra

Abstract

Three possible methods for computing the spectra of the mixed mercury dihalides, HgCll, HgBrl, and HgBrCl, free from contributions of other species, are described and discussed as to their general applicability. The spectra studied are either those of equimolar mixtures of HgX₂ and HgY₂, or of HgX₂ with added halide Y^–. A new procedure is described for computing the formation constants of these species and the spectra have been resolved into their component bands. Each species is shown to contain three bands, even though this is not always apparent from inspection of the calculated spectra. Peak maxima have been found at 37 800, 46 600, and 53 400 for HgCll, 37 800, 43 200, and 51 210 for HgBrl, and 43 500, 47 400, and 57 200 cm^–1 for HgBrCl. The other parameters of the resolved bands are given.