Introduction to Electronic Spectroscopy and Structure

Despite the fact that we treated vibrational and rotational spectroscopy first, the astute student will recognize that one of the mysteries of classical mechanics involved electronic spectroscopy. The inability to explain the (electronic) spectrum of the hydrogen atom was a major reason for the development of quantum mechanics. Yet, we have put off a detailed discussion of it until after considering rotational and vibrational spectra. 

The reason for the delay is that a detailed discussion is slightly more complicated for electronic spectra than for rotations or vibrations. Some new ideas will have to be developed in order to begin to understand the electronic spectra and structures of many-electron systems. (We should recognize that the electronic spectrum of hydrogen, even in the formalism of quantum mechanics, will be relatively simple.) fiowever, as with rotational and vibrational spectroscopy, our treatment of electronic spectroscopy in this chapter is limited by necessity. Entire books are written on the subject, and we can only introduce some basic ideas here. 

Unless otheiwise noted, all art on this page is Cengage Learning 2014. 

As with rotational and vibrational transitions, there is a selection rule for electronic transitions dictating which electronic wavefunctions participate in allowed transitions. Allowed electronic transitions must have a nonzero transition moment as given by the expression 

Unfortunately, for electronic transitions, gross selection rules are not as straightforward to define. Therefore, we will consider the selection rules for electronic transitions as they arise in the discussion of the material. The electronic spectrum of the hydrogen atom, for example, has a relatively simple selection rule. The electronic spectrum of the benzene molecule, as a counter-example, follows more complex rules. 

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Advanced synchrotron based characterization techniques of solid state applied to macromolecules are reported in Chapter 4. After an introduction to the physics and principles of NEXAFS and XPS spectroscopy, the main features of these techniques that allow a non conventional assessment of the electronic and chemical structure are depicted. The study of macromolecular organization and self-assembly can be nicely obtained by these spectroscopic tools. For example the formation of SAMs (Self Assembled Monolayers) of a variety of molecules arranged in supramolecular assemblies can be detected as well as the behaviour of biomolecules bound to surfaces mimicking biological substrates. Many examples of macromolecules studied with NEXAFS and XPS highlight the potential of these spectroscopic methods to give insight into the molecular and supramolecular structure which in turn determine the most desired properties. 

It is no exaggCTation to say that the development of structure characterization techniques for molecular solids has revolutionized the study of organic solid state chemistry. It has allowed for the first time a rationalization of observed properties and transformations (including reactivity) which were previously unexplained by simple chemical means. The principal method used has been diffraction, particularly of X-rays, but also, more recently, of electrons and neutrons. This chapter will first give a basic introduction to crystal symmetry and then describe the use of X-ray, neutron, and electron diffraction, as well as of EXAFS and of vibrational spectroscopy in the study of molecular crystals. 

Electron paramagnetic resonance spectroscopy (HER), also called electron spin resonance spectroscopy (ESR), may be used for direct detection and conformational and structural characterization of paramagnetic species. Good introductions to F.PR have been provided by Fischer8 and I.effler9 and most books on radical chemistry have a section on EPR. EPR detection limits arc dependent on radical structure and the signal complexity. However, with modern instrumentation, radical concentrations > 1 O 9 M can be detected and concentrations > I0"7 M can be reliably quantified. 

The purpose of this article is to review studies carried out on hemes incorporated inside the micellar cavity, and examine the effect of micellar interaction on the electronic and structural properties of the heme. A comparison of these results with those on the metalloproteins is clearly in order to assess their suitability as models. The article begins with a general introduction to micellar properties, the incorporation of hemes in the micellar cavity, and then discusses results on hemes inside the micelles with different oxidation and spin states, and stereochemistry. The experimental techniques used in the studies on these aqueous detergent micelles are mostly NMR and optical spectroscopy. The present article has therefore a strong emphasis on NMR spectroscopy, since this technique has been used very extensively and purposefully for studies on hemes inside micellar cavities. 

Annelation on to a benzene ring increases considerably the complexity of the spectra, and indole has absorptions at 216 (4.54), 266 sh (3.76), 270 (3.77), 276 (3.76), 278 (3.76) and 287 (3.68) nm in ethanol solution. Because of the widespread occurrence of the indole ring system in nature and the sensitivity of absorption band position and intensity to substitution type, considerable use has been made of electronic spectroscopy in the past for structure identification. An extensive tabulation of data, primarily for monosubstituted derivatives, is available (71PMH(3)67,p.94). As expected, whereas the effects of alkylation are comparatively slight, introduction of groups capable of mesomeric interaction with the indole it -system may cause profound changes in the appearance of the spectrum representative examples are given in Table 24. 

A number of reviews can be consulted for an introduction to the fundamentals both theoretical and practical covering XPS. These include Riggs and Parker (2) and the book by Carlson (3). Electron spectroscopy is reviewed in alternate years in the Fundamental Reviews issue of Analytical Chemistry. The last literature review was published in 1980 (4) and this and previous reviews can be consulted for a coverage of all aspects of the literature of XPS. A number of recent symposia have been held on applications of surface analytical methods in various aspects of materials science such as the symposium on characterization of molecular structures of polymers by photon, electron, and ion probes at the March 1980 American Chemical Society meetings in Houston ( 5) and the International Symposium on Physiochemical Aspects of Polymer Surfaces at this meeting as well as the symposium on industrial applications of surface analysis of which this article is a part. Review articles on various applications of XPS in materials science are listed in Table I. 

When my interest returned and we began researching the analytical applications of CD in the 70 s, I felt I had a head start. But there was so much that was new. A great deal had happened to CD over the years as it matured and expanded to include the far-UV the study of optical activity in excited state emissions, and in vibrational and Raman spectroscopy and the evolution of new empirical models applicable to the interpretation of the structural properties of macromolecules. Most important of all, perhaps, was the arrival of high tech electronics and materials which had brought CD instrumentation out of the dark ages. And now, ironically, almost 35 years after my introduction to CD, my special interest is the exploitation of chiral transition metal complexes as chirality induction reagents in chemical analysis. 

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