UV-visible molecular absorption

J. C. Travis et al., Intrinsic Wavelength Standard Absorption Bands in Holmium Oxide Solution for UV/Visible Molecular Absorption Spectrophotometry, J. Phys. Chem. Ref. Data 2005,34, 41. 

Ultraviolet and risible, absorption measurements are widely used for the identification and determination of many different inorganic and organic species. In fact, UV-visible molecular absorption methods are probably the most widely used of all quantitative analysis techniques in chemical, environmental, forensic, and clinical laboratories throughout the world. 

Empirically, molar absorptivities (e values) that range from zero up to a maximum on the order of lO L mol cm are observed in UV-visible molecular absorption spectrometry. For any particular absorption maximum, the magnitude of e depends on the capture cross section (Section 13B, Equation 13-5) of the species and the probability for an energy-absorbing transition to occur. The relationship between e and these variables has been shown to be... 

Absorption Absorbance or the ratio of transmitted to incident radiant power, A = -log(( /( o) Atomic absorption, UV-visible molecular absorption, IR absorption... 

GC, gas chromatography HPLC, high-performance liquid chromatography MS, mass spectroscopy AA, atomic absorption GFAA, graphite furnace atomic absorption ICP, inductively coupled plasma UV-VIS, ultraviolet-visible molecular absorption spectroscopy IC, ion chromatography. 

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. 

Materials characterization techniques, ie, atomic and molecular identification and analysis, ate discussed ia articles the tides of which, for the most part, are descriptive of the analytical method. For example, both iaftared (it) and near iaftared analysis (nira) are described ia Infrared and raman SPECTROSCOPY. Nucleai magaetic resoaance (nmr) and electron spia resonance (esr) are discussed ia Magnetic spin resonance. Ultraviolet (uv) and visible (vis), absorption and emission, as well as Raman spectroscopy, circular dichroism (cd), etc are discussed ia Spectroscopy (see also Chemiluminescence Electho-analytical techniques It unoassay Mass specthot thy Microscopy Microwave technology Plasma technology and X-ray technology). 

Electronic spectroscopy, often referred to as UV/visible spectroscopy, is a useful instrumental technique for characterising the colours of dyes and pigments. These spectra may be obtained from appropriate samples either in transmission (absorption) or reflection mode. UY/visible absorption spectra of dyes in solution, such as that illustrated in Figure 2.3, provide important information to enable relationships between the colour and the molecular structure of the dyes to be developed. 

The absorption of electromagnetic radiation by molecular species in solution in the UV/visible region is followed by relaxation from excited electronic states to the ground state mostly by a combination of radiationless processes. Vibrational relaxation, where the excess energy is rapidly dis-... 

The conformational mobility of a chromophoric main-chain polymer is often connected to its electronic structure. Therefore, changes in the UV-visible absorption spectra and/or chiroptical properties are spectroscopically observable as thermo-, solvato-, piezo-, or electrochromisms. It is widely reported that o-conjugating polysilanes exhibit these phenomena remarkably clearly.34 However, their structural origins were controversial until recently, since limited information was available on the correlation between the conformational properties of the main chain, electronic state, and (chir)optical characteristics. In 1996, we reported that in various polysilanes in tetrahydrofuran (THF) at 30°C, the main-chain peak intensity per silicon repeat unit, e (Si repeat unit)-1 dm3 cm-1, increases exponentially as the viscosity index, a, increases.41 Although conventional viscometric measurements often requires a wide range of low-dispersity molecular-weight polymer samples, a size exclusion chromatography (SEC) machine equipped with a viscometric detector can afford... 

A series of aggregation structures of bilayer forming azobenzene amphiphiles, CnAzoCmN+Br, both in single crystals and cast films was determined by the X-ray diffraction method and uv-visible absorption spectroscopy. From the relationship between chemical structures and their two-dimensional supramolecular structure, factors determining the molecular orientation in bilayer structure were discussed. Some unique properties based on two-dimensional molecular ordering were also discussed. 

In this paper, UV-visible absorption spectra and X-ray diffraction experiments of single crystals and solvent cast films of the azobenzene amphiphiles, CnAzoCmN+Br, were systematically investigated. Structural characterization of the cast bilayer films are discussed in comparison with aqueous solutions and single crystals. Some novel functional properties of the cast films are described, too. We also emphasize that the two-dimensional molecular assemblies, cast films and crystals of bilayer-forming amphiphiles, are suitable candidates for "crystal engineering" because of their simple structures compared with usual three-dimensional molecular crystals. 

Although this example, at face value, looks to be a case of the use of the absorption of UV/visible radiation to determine the concentration of a single ionic species (the Cu2+ ion) in solution, and, therefore, the province of the previous chapter, it is, in fact, the quantification of a molecular absorption band. In a sulfate solution, the copper ion actually exists, not as a bare ion, but as the pentaquo species, in which the central copper ion is surrounded by five water molecules and a sulfate ion in an octahedral structure (Fig. 4.1). The color of the transition metal ions arises directly from the interaction between the outer d orbital electrons of the transition metal and the electric field created by the presence of these co-ordinating molecules (called ligands). Without the aquation... 

The UV-visible absorption and emission spectra and excited state lifetimes of polymers are sensitive to chemical structure, polymer conformation and molecular environment and thus information concerning these properties is accessible by electronic spectroscopy measurements (4-6). One example of the application of such measurements is given in Figure 3 which illustrates the possible energy dissipation pathways which can occur in a polymer containing aromatic side groups following absorption of radiation. 

The nitrosonium cation bears a formal relationship to the well-studied halogens (i.e. X2 = I2, Br2, and Cl2), with both classes of structurally simple diatomic electron acceptors forming an extensive series of intermolecular electron donor-acceptor (EDA) complexes that show well-defined charge-transfer absorption bands in the UV-visible spectral region. Mulliken (1952a,b 1964 Mulliken and Person, 1969) originally identified the three possible nonbonded structures of the halogen complexes as in Chart 7, and the subsequent X-ray studies established the axial form II to be extant in the crystals of the benzene complexes with Cl2 and Br2 (Hassel and Stromme, 1958, 1959). In these 1 1 molecular complexes, the closest approach of the... 

Chapter 1 is an introduction to the field of molecular fluorescence, starting with a short history of fluorescence. In Chapter 2, the various aspects of light absorption (electronic transitions, UV-visible spectrophotometry) are reviewed. 

The different molecular species present in a palladium nitrate solution can be easily identified by UV-visible spectroscopy (Fig. 13.2). Two absorption peaks are generally observed at A, = 285 nm and A = 378 nm, the latter being ascribed to free nitrate ions corresponding to the electronic transition from the a to the it state in the NOs ions, as observed in the case of an aqueous solution of NaNOs. The other absorption band at A = 285 nm is assigned to a d-d transition in the aquo complex Pd(H20)4 These UV-visible results show the noncomplexant behavior of nitrate ions toward palladium metallic centers. The palladium containing species in the starting solution is then the planar tetra-aquo complex Pd(H20)4 +. 

In comparison to UV-visible spectroscopy, IR absorption bands can be of great assistance in determining the molecular structure of a compound and of less importance for quantitative analysis. 

---