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Optica Publishing Group
  • Applied Spectroscopy
  • Vol. 47,
  • Issue 10,
  • pp. 1712-1715
  • (1993)

Approach for Increased Information from the Second-Derivative Spectra in UV-Vis Absorption Spectroscopy

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Abstract

The resolution of overlapping bands in the UV-Vis absorption spectra leading to determination of their basic parameters (ν<sub>max</sub>, ɛ<sub>max</sub>, Δν<sub>1/2</sub>) provides important information about the energies and probabilities of the electronic transitions. In the analysis of UV-Vis absorption spectra recorded linearly in wavelength by means of modern spectrophotometers with holographic gratings, the analytical shape describing individual bands is asymmetric. This factor leads to certain limitations in determining their number with the use of the second-derivative spectra and decreased effectiveness of the computing procedure. It was found that the loss of information in d<sup>2</sup><i>A</i>/dλ<sup>2</sup> is due to its long-wavelength attenuation in comparison with d<sup>2</sup><i>A</i>/dν<sup>2</sup>. An analytical equation connecting d<sup>2</sup><i>A</i>/dλ<sup>2</sup> with d<sup>2</sup><i>A</i>/dν<sup>2</sup> is proposed, which restores the information from the second derivative in the long-wavelength region.

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