Atomic theory electromagnetic radiation

Although shown to have some serious flaws and long since abandoned, the Bohr model laid the groundwork for the more sophisticated theories of atomic structure that are accepted today and introduced the all-important concept that only specific energy states are allowed for an electron in an atom. Like electromagnetic radiation, electrons in atoms are now visualized as having a dual wave/particle nature. 

These speculations about the ionic, polar, or electronic nature of chemical bonding, which arose largely from solution theory, resulted mostly in static models of the chemical bond or atom structure. In contrast is another tradition, which is more closely identified with ether theory and electrodynamics. This tradition, too, may be associated with Helmholtz, especially by way of his contributions to nineteenth-century theories of a "vortex atom" that would explain chemical affinities as well as the origin of electromagnetism, radiation, and spectral lines. 

The interaction processes between UV-Vis photons and the outer electrons of the atoms of the analytes can be understood using quantum mechanics theory. In the thermodynamic equilibrium between matter and interacting electromagnetic radiation, according to the radiation laws postulated by Einstein, three basic processes between two stable energy levels 1 and 2 are possible. These processes, which can be defined by their corresponding transition probabilities, are summarised in Figure 1.3. 

Binary and ternary spectra. We will be concerned mainly with absorption of electromagnetic radiation by binary complexes of inert atoms and/or simple molecules. For such systems, high-quality measurements of collision-induced spectra exist, which will be reviewed in Chapter 3. Furthermore, a rigorous, theoretical description of binary systems and spectra is possible which lends itself readily to numerical calculations, Chapters 5 and 6. Measurements of binary spectra may be directly compared with the fundamental theory. Interesting experimental and theoretical studies of various aspects of ternary spectra are also possible. These are aimed, for example, at a distinction of the fairly well understood pairwise-additive dipole components and the less well understood irreducible three-body induced components. Induced spectra of bigger complexes, and of reactive systems, are also of interest and will be considered to some limited extent below. 

We now consider the effect of exposing a system to electromagnetic radiation. Our treatment will involve approximations beyond that of replacing (3.13) with (3.16). A proper treatment of the interaction of radiation with matter must treat both the atom and the radiation field quantum-mechanically this gives what is called quantum field theory (or quantum electrodynamics). However, the quantum theory of radiation is beyond the scope of this book. We will treat the atom quantum-mechanically, but will treat the radiation field as a classical wave, ignoring its photon aspect. Thus our treatment is semiclassical. 

There are several reasons for starting this account with a discussion of electromagnetic radiation. Historically, it was in this area that the quantum theory first developed. It is easier here to understand the evidence for the theory, and to appreciate some of its paradoxical consequences, than it is in the quantum theory of matter. The applications of the light-quantum hypothesis, as it was first called, also provide key pieces of evidence for the quantization of energy in atoms and molecules. Studies of the absorption and emission of radiation—the field of spectroscopy—and of the effect of light on chemical reactions—photochemistry—are very important areas of modem chemistry, in which the quantum nature of radiation is crucial. 

The theory gives rise to a concept of atomic or molecular orbital, ie the wave-function, which depends explicitly on the spatial coordinates of only one electron and the quantum numbers that define energy, spin, orbital momentum, and symmetry properties of the two last wavefunctions. Quantum numbers of the wavefunc-tions in lower and upper states determine the possible interaction of the entity with electromagnetic radiation [1],... 

If you recall from the beginning of this chapter, some of the work that led to the development of the modem atomic theory was done by scientists Max Planck, Albert Einstein, Louis de Broglie, Werner Heisenberg, Niels Bohr, and Erwin Shrodinger. The first work centered around light (electromagnetic radiation), while the later work focused on the wave-like nature of matter. The AP test does not probe too deeply into the theoretical considerations of any of these scientists, but some calculations have popped up on previous tests. Therefore, let s turn our attention to some of the equations associated with these scientists work. 

The interaction between electromagnetic radiation and atoms or molecules is now discussed by empirical methods, then by semiclassical arguments, and finally by quantum theory. 

In the classical theory of electrodynamics, electromagnetic radiation is emitted when an electron moves in its orbit but, ac cording to the Bohr theory of the atom,... 

The last quantum number was proposed to solve a mystery. Emission spectroscopy measures the wavelengths of the electromagnetic radiation emitted when an electron in an atom drops from a higher-energy state to a lower one. Spectroscopists noticed that some spectral lines split into two lines when theory predicted that only one should exist. A new quantum property and number were needed to explain spectral splitting. At the time, the electron was considered a particle, and scientists called this new property spin, usually designated as ms. The spin quantum number can have only two possible values, +1/2 or -1/2. It is usually depicted as an arrow pointing either up or down. 

The first theoretical model of optical activity was proposed by Drude in 1896. It postulates that charged particles (i.e., electrons), if present in a dissymmetric environment, are constrained to move in a helical path. Optical activity was a physical consequence of the interaction between electromagnetic radiation and the helical electronic field. Early theoretical attempts to combine molecular geometric models, such as the tetrahedral carbon atom, with the physical model of Drude were based on the use of coupled oscillators and molecular polarizabilities to explain optical activity. All subsequent quantum mechanical approaches were, and still are, based on perturbation theory. Most theoretical treatments are really semiclassical because quantum theories require so many simplifications and assumptions that their practical applications are limited to the point that there is still no comprehensive theory that allows for the predetermination of the sign and magnitude of molecular optical activity. 

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