Ultraviolet-visible spectroscopy difference spectra

The preceding empirical measures have taken chemical reactions as model processes. Now we consider a different class of model process, namely, a transition from one energy level to another within a molecule. The various forms of spectroscopy allow us to observe these transitions thus, electronic transitions give rise to ultraviolet—visible absorption spectra and fluorescence spectra. Because of solute-solvent interactions, the electronic energy levels of a solute are influenced by the solvent in which it is dissolved therefore, the absorption and fluorescence spectra contain information about the solute-solvent interactions. A change in electronic absorption spectrum caused by a change in the solvent is called solvatochromism. 

In the columns identifying the experimental method, MW stands for any method studying the pure rotational spectrum of a molecule except for rotational Raman spectroscopy marked by the rot. Raman entry. FUR stands for Fourier transform infhired spectroscopy, IR laser for any infiured laser system (diode laser, difference frequency laser or other). LIF indicates laser induced fluorescence usually in the visible or ultraviolet region of the spectrum, joint marks a few selected cases where spectroscopic and diffraction data were used to determine the molecular structure. A method enclosed in parentheses means that the structure has been derived from data that were collected by this method in earlier publications. The type of structure determined is shown by the symbols identifying the various methods discussed in section II. V/ refers to determinations using the Kraitchman/Chutjian expressions or least squares methods fitting only isotopic differences of principal or planar moments (with or without first... 

The ultraviolet-visible spectra of most compounds are of limited value for qualitative analysis and have been largely superseded by the more definitive infrared and mass spectroscopies. Qualitative analytical use of ultraviolet-visible spectra has largely involved describing compounds in terms of the positions and molar absorptivities of their absorption maxima, occasionally including their absorption minima. Indeed, some organic compounds are still characterized in terms of the number of peaks in the UV-visible spectrum and their absorbance ratios. This is usually the case in phytochemistry and photodiode array chromatography and when the analyst has a limited range of compounds to work with whose spectra are known to differ. In the pharmacopeias, however, absorbance ratios have found use in identity tests, and are referred to as Q-values in the U.S. Pharmacopia (USP). 

Infrared spectra differ markedly from the typical ultraviolet or visible spectrum. Infrared spectra are marked by many relatively sharp peaks and the spectra for different compounds are quite different. This makes infrared spectroscopy ideal for qualitative analysis of organic compounds. 

Atomic emission spectroscopy is one of the oldest instrumental techniques used for chemical analysis. It is used to study the transitions between electronic energy levels in atoms or ions. These energy differences are usually in the visible region (400-700 nm) of the electromagnetic spectrum, but if the energy difference is larger, then the transitions may lie in the ultraviolet region. 

Ultraviolet Spectroscopy The ultraviolet spectra of aromatic compounds are quite different from those of nonaromatic polyenes. For example, benzene has three absorptions in the ultraviolet region an intense band at Amax = 184 nm (e = 68,000), a moderate band at Amax = 204 nm (e = 8800), and a characteristic low-intensity band of multiple absorptions centered around 254 nm (e = 200 to 300). In the UV spectrum of benzene in Figure 16-19, the absorption at 184 nm does not appear because wavelengths shorter than 200 nm are not accessible by standard UV-visible spectrometers. 

CD spectroscopy measures the difference in absorbance between left- and right-circularly polarized incident radiation, in the near ultraviolet to visible and infrared regions of the spectrum. 

U V- Vis. Spectroscopic measurements in the ultraviolet and visible range of the electronic spectrum (UV-Vis) can be used to probe electronic transitions in certain metal atoms and ion complexes. The energy of an electronic transition can depend upon the symmetry of the metal ion being different for transitions in a metal complex displaying tetrahedral (Td) symmetry from the same metal showing an octahedral (Oh) symmetry. Thus, it is possible to use UV-Vis spectroscopy to interrogate the symmetry of certain metal ions bound to oxide surfaces. We show here a few examples of the use of UV-Vis spectroscopy to characterized supported metal oxides. 

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