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Absorption Spectra and Termination Kinetics of Transient Free Radicals in Solution Observed by UV./VIS. Spectroscopy with modulated excitation
Author(s) -
Huggenberger Christian,
Fischer Hanns
Publication year - 1981
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19810640134
Subject(s) - chemistry , radical , photochemistry , absorbance , kinetics , photodissociation , spectroscopy , ultrafast laser spectroscopy , excitation , absorption spectroscopy , spectral line , absorption (acoustics) , wavelength , analytical chemistry (journal) , organic chemistry , optics , chromatography , physics , quantum mechanics , astronomy , electrical engineering , engineering
Free radicals are generated in liquid solutions by harmonically modulated photolysis of suitable substrates. Harmonic analysis of the absorbance as functions of wavelength and modulation frequency yields the optical spectra and the decay kinetics of the transient species. The experimental technique and the analysis are described in detail. Results on t ‐butyl, 2‐propyl and benzyl radicals generated by photolysis of the corresponding dialkyl resp. dibenzyl ketones are reported. They confirm previous spectral assignments and show that the termination reactions are diffusion controlled.