Electrophilic Character of the Hg 6(3P1) Atom and the Mechanism of Electronic Energy Transfer in Mercury Photosensitization

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Abstract
It is shown that in mercury‐6(3P1)‐photosensitized reactions the Hg 6(3P1) atom behaves as a distinctly electrophilic reactant in most of its reactions and that the H/D isotope effect exhibited by some paraffin molecules with respect to the quenching reaction can be satisfactorily estimated from transition‐state theory. This interpretation of the data, taken in conjunction with the results of some recent primary process studies, point up the chemical nature of electronic energy‐transfer processes in these systems in that the transfer reaction proceeds through the formation of a well‐defined transition complex involving both substrate molecule and sensitizer atom.