Molecular absorption spectroscopy principles

In this chapter, we discuss the basic principles that are necessary to understand measurements made with electromagnetic radiation, particularly those deeding with the absorption of UV, visible, and IR radiation. The nature of electromagnetic radiation and its interactions with matter are stressed. The next four chapters are devoted to. spectroscopic instruments (Chapter 25), molecular absorption spectroscopy (Chapter 26), molecular fluorescence spectroscopy (Chapter 27), and atomic spectroscopy (Chapter 28). 

Spectroscopic Methods. HO and the other peroxy radicals have characteristic absorptions due to various molecular processes. In principle, these spectroscopic features could be used to determine atmospheric concentrations of peroxy radicals. The discussion of spectroscopic techniques in the measurement of peroxy radicals is divided into descriptions of specific spectral regions. General issues related to the use of spectroscopy for quantitative analysis are presented next. 

Metals can be conveniently determined by emission spectroscopy using inductively coupled plasma (ICP). A great advantage of ICP emission spectroscopy as applied to environmental analysis is that several metals can be determined simultaneously by this method. Thus, multielement analysis of unknown samples can be performed rapidly by this technique. Another advantage is that, unlike atomic absorption spectroscopy, the chemical interference in this method is very low. Chemical interferences are generally attributed to the formation of molecular compounds (from the atoms) as well as to ionization and thermochemical effects. The principle of the ICP method is described below. 

With reference to absorption spectroscopy, we deal here with photon absorption by electrons distributed within specific orbitals in a population of molecules. Upon absorption, one electron reaches an upper vacant orbital of higher energy. Thus, light absorption would induce the molecule excitation. Transition from ground to excited state is accompanied by a redistribution of an electronic cloud within the molecular orbitals. This condition is implicit for transitions to occur. According to the Franck-Condon principle, electronic transitions are so fast that they occur without any change in nuclei position, that is, nuclei have no time to move during electronic transition. For this reason, electronic transitions are always drawn as vertical lines. 

In the first section, steady-state spectroscopy is used to determine the stoichiometry and association constants of molecular ensembles, emphasize the changes due to light irradiation and provide information on the existence of photoinduced processes. Investigation of the dynamics of photoinduced processes, i.e. the determination of the rate constants for these processes, is best done with time-resolved techniques aiming at determining the temporal evolution of absorbance or fluorescence intensity (or anisotropy). The principles of these techniques (pulse fluorometry, phase-modulation fluorometry, transient absorption spectroscopy) will be described, and in each case pertinent examples of applications in the flelds of supramolecular photophysics and photochemistry will be presented. 

To observe particular rotational isomeric states, the method must be much more rapid than the rate of conformational isomerization. Optical methods such as absorption spectroscopy or light-scattering spectroscopy provide a short-time probe of the molecular conformation. If the electronic states of the molecule are strongly coupled to the backbone conformation, the ultraviolet or visible spectrum of the molecule can be used to study the conformational composition. The vibrational states of macromolecules are often coupled to the backbone conformation. The frequencies of molecular vibrations can be determined by infrared absorption spectroscopy and Raman scattering spectroscopy. The basic principles of vibrational spectres-... 

The quantum theory of spectral collapse presented in Chapter 4 aims at even lower gas densities where the Stark or Zeeman multiplets of atomic spectra as well as the rotational structure of all the branches of absorption or Raman spectra are well resolved. The evolution of basic ideas of line broadening and interference (spectral exchange) is reviewed. Adiabatic and non-adiabatic spectral broadening are described in the frame of binary non-Markovian theory and compared with the impact approximation. The conditions for spectral collapse and subsequent narrowing of the spectra are analysed for the simplest examples, which model typical situations in atomic and molecular spectroscopy. Special attention is paid to collapse of the isotropic Raman spectrum. Quantum theory, based on first principles, attempts to predict the. /-dependence of the widths of the rotational component as well as the envelope of the unresolved and then collapsed spectrum (Fig. 0.4). 

The signal generation principle of Raman is inelastic molecular light scattering, in contrast to resonant energy absorption/emission in IR spectroscopy. During the measurement, the sample is irradiated with intense monochromatic radiation. While most of this radiation is transmitted, refracted or reflected, a small amount is scattered at the molecules. 

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