Directional nature of light absorption

Figure 3.12 Directional nature of light absorption in H2 molecule.

Let the coordinate system be such as that given in Figure 4. IS. The electric vectors of a plane polarized radiation vibrate along OZ in the ZX plane and OX is the direction of propagation of the plane polarized wave. When a solution of anisotropic molecules is exposed to this plane polarized radiation, the electric vector will find the solute molecules in random orientation. Only those molecules absorb with maximum probability which have their transition moment oriented parallel to OZ (photoselection). Those molecules which are oriented by an angle 6 to this direction will have their absorption probability reduced by a factor cos 6, and the intensity of absorption by cos2 6. Finally, the molecules oriented perpendicular to the electric vector will not absorb at all. These statements are direct consequences of directional nature of light absorption... 

Now it becomes increasingly clear that selectivity can be achieved in photochemical reactions. This is due to highly selective nature of light absorption which allows injection of energy into particular bonds of particular molecule. Under proper conditions, photochemistry may provide a short route for the synthesis of systems which are essentially unavailable by alternate synthetic methods. The development of spectroscopic techniques provides the way for direct study of transient intermediates. In this manner photochemistry gets today s face. 

In 1917 Einstein [18] wrote a paper on the dualistic nature of light in which he discusses emission without excitation from external causes, in other words stimulated emission and also spontaneous absorption and emission. He derives Planck s formula but also discusses the recoil of molecules when they emit photons. It is the latter discussion that Einstein regarded as the most significant aspect of the paper If a radiation bundle has the effect that a molecule struck by it absorbs or emits a quantity of energy hv in the form of radiation (ingoing radiation), then a momentum hvlc is always transferred to the molecule. For an absorption of energy, this takes place in the direction of propagation of the radiation bundle for an emission, in the opposite direction. ... 

The extinction I is proportional to the concentration C of light absorbers in the medium and the directional nature of absorption in an anisotropic medium is denoted by the vector g, known as the molar extinction. Because Equation 6.8 was derived for a wave propagating in the vacuum, the contribution of the extinction to the light intensity is lost in Equation 6.7. For an optical wave propagating in an isotropic medium, Equation 6.7 can be rewritten in the form of Equation 6.10. 

LASER is an acronym that stands for Light Amplification by Stimulated Emission of Radiation. The laser produces an intense, highly directional beam of light. The most common cause of laser-induced tissue damage is thermal in nature, where the tissue proteins are denatured due to the temperature rise following absorption of laser energy. The human body is vulnerable to the output of certain lasers, and under certain circumstances, exposure can result in damage to the eye and skin. 

A second way to overcome the high reactivity of carbenes and so permit their direct observation is to conduct an experiment on a very short timescale. In the past five years this approach has been applied to a number of aromatic carbenes. These experiments rely on the rapid photochemical generation of the carbene with a short pulse of light (the pump beam), and the detection of the optical absorption (or emission) of the carbene with a probe beam. These pump-probe experiments can be performed on timescales ranging from picoseconds to milliseconds. They provide an important opportunity absent from the low temperature experiments, namely, the capability of studying chemical reactions of the carbene under normal conditions. Before proceeding to discuss the application of these techniques to aromatic carbenes, a few details illuminating the nature of the data obtained and the limitations of the experiment need to be introduced. 

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