Ultraviolet/visible spectroscopy extinction coefficient

Ultraviolet-Visible Spectroscopy Ultraviolet-visible (UV-VIS) molecular absorption spectrophotometry (often called light absorption spectrophotometry or just UV-visible spectrophotometry) is a technique based on measuring the absorption of near-UV or visible radiation (180-770 nm) by molecules in solution.35,36 Reference standard characterization by UV-VIS spectophotometry includes determining the absorption spectra and the molar extinction coefficient. These two spectral characterizations are used as identifiers of reference standards. 

Low-temperature, photoaggregation techniques employing ultraviolet-visible absorption spectroscopy have also been used to evaluate extinction coefficients relative to silver atoms for diatomic and triatomic silver in Ar and Kr matrices at 10-12 K 149). Such data are of fundamental importance in quantitative studies of the chemistry and photochemistry of metal-atom clusters and in the analysis of metal-atom recombination-kinetics. In essence, simple, mass-balance considerations in a photoaggregation experiment lead to the following expression, which relates the decrease in an atomic absorption to increases in diatomic and triatomic absorptions in terms of the appropriate extinction coefficients. 

In connection with visible-ultraviolet spectroscopy, know the meaning of nanometer, electronic transition, Beer s law, molar absorptivity or extinction coefficient. 

Ultraviolet and visible absorption spectroscopy has been a powerful aid to studies of free radicals in the gas phase but is of less value in the solid phase because of line broadening and consequent lack of resolution. Under suitable conditions, however, solid state infrared spectra can give information on the structure of free radicals and on the forces holding the constituent atoms in their equilibrium positions. The technique is less sensitive than e.s.r. because the extinction coefficients of vibrational transitions are generally low but the ability to observe non-para-magnetic molecules in addition to free radicals is sometimes advantageous. 

The application of ultraviolet and visible spectroscopy to the identification and measurement of carbenium ions derived from aromatic and dienic monomer has already been discussed (see Sect. II-G-2). The use of this technique to monitor stable carbenium salts is also well known. We have finally stressed in a preceding section that the fate of certain anions could be followed spectrophotometrically during a cationic polymerisation. The limits of detection allowed by the values of the extinction coefficients of all these species and by the sensitivity of present-day instruments is 10 to 10 M. 

Spectroscopy in the ultraviolet and visible range has been used to follow the evolution of NO2 in order to study the autoxidation kinetics (29), and symmetric NO3 has been characterized by the method already in the early twentieth century (5,48) it can be prepared in easily detectable quantities by the reaction of N2O5 or NO2 with ozone. It is, however, not very fikely an intermediate of NO autoxidation, because its formation would require the splitting of02, and because the electrode potential ofits reduction to NOs" has been estimated to be higher than 2 V, which would lead to side reactions that would have been hardly overlooked. In contrast, the electronic spectrum of ONOO is not known, and it would most likely not be helpfijl in detecting it at steady-state concentrations, since known extinction coefficients of N-O compounds in the visible and near ultraviolet spectrum are all below 1000 cm Thus, the absorption of ONOO during autoxidation would vanish under the contribution of the product, NO2. ... 

Ultraviolet and visible spectroscopy gives a way of estimating the extent of conjugation in a molecule. Peaks in electronic spectra are usually broad and are reported as (nm). Their relative intensities are given by the molar absorptivity (extinction coefficient) e. 

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