Ultraviolet and Visible Absorption Spectroscopy

Absorbing species Absorption of ultraviolet and visible radiation by molecules generally occurs in one or more electronic absorption bands, each of which is made up of many closely packed but discrete lines. Each line arises from the transition of an electron from the ground state to one of many vibrational and rotational energy states associated with each excited electronic energy state. Because there are so many of these vibrational and rotational states and because their energies differ only slightly, the number of lines contained in the typical band is quite large and their displacement from one very small. Absorption by organic compounds Absorption of radiation by organic molecules in the wavelength region between 180 and 780 nm results from interactions between photons and electrons that either participate directly in bond formation (and are thus associated with more than one atom) or are localized about such atoms as oxygen, sulfur, nitrogen, and the halogens. The wavelength at which an organic molecule absorbs depends on how tightly its electrons are bound. The shared electrons in carbon/carbon or carbon/hydrogen single bonds are so firmly held that there excitation requires energies corresponding to wavelengths in the vacuum ultraviolet region below 180 nm. Electrons involved in double and triple bonds of organic molecules are not as strongly held and are therefore more easily excited by radiation; thus, species with unsaturated bonds generally exhibit useful absorption peaks. Unsaturated organic functional groups that absorb in the ultraviolet or visible regions are known as chromophores. Chromophores are unsaturated organic functional groups that absorb in the ultraviolet or visible region. The data for position and peak intensity can serve only as a rough guide for identification purposes, since both are influenced by solvent effects as well as other structural details of the molecule. In addition, conjugation between two or more chromophores tends to cause shifts in peak maxima to longer wavelengths. Finally, vibrational effects broaden absorption peaks in the ultraviolet and visible regions, which often makes precise determination of an absorption maximum difficult. Saturated organic compunds containing heteroatoms such as oxygen, nitrogen, sulfur, or halogens have non-bonding electrons that can be excited by radiation in the 170 to 250 nm range. Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3

Some of these compounds, such as alcohols and ethers, are common solvents, so their absorption in this region prevents measuring absorption of analytes dissolved in these compounds at wavelengths shorter than 180 to 200 nm. Occasionally, absorption in this region is used for determining halogen- and sulfur- bearing compounds. Absorption by Inorganic Species The ions and complexes of elements in the first two transition series absorb broad bands of visible radiation in at least one of their oxidation states and are, as a result, coloured. Absorption involves transitions between filled and unfilled d-orbitals with energies that depend on the ligands bonded to the metal ions. The energy differences between these d-orbitals (and thus the position of the corresponding absorption peak) depend on the position of the element in the periodic table, its oxidation state, and the nature of the ligand bonded to it. Charge-transfer complex Charge transfer is particularly important because molar absorptivities are unusually large ( > 1000), which leads to high sensitivity. Many inorganic and organic complexes exhibit this type of absorption and are therefore called charge-transfer complexes. A charge-transfer complex consists of an electron-donor group bonded to an electron acceptor. When this product absorbs radiation, an electron from the donor is transferred to an orbital that is largely associated with the acceptor.

Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3