Vibrational spectroscopy.docVIP

Vibrational spectroscopy: infra-red and Raman spectroscopy 5.l FUNDAMENTALS OF VIBRATIONAL SPECTROSCOPY Vibrational spectroscopy is concerned with the detection of transitions between energy levels in molecules that result from stretching and bending vibrations of the interatomic bonds. The vibrational frequencies are shown to be characteristic of particular functional groups in molecules. They are sensitive to the molecular environment, chain conformations and morphology and so afford a useful method for polymer analysis. When used either alone or in conjunction with other physicochemical techniques vibrational spectroscopy is capable of providing detailed information on polymer structure [1.2]. It follows that, in attempting to identify and characterize polymeric materials, almost invariably recourse will be made to some form of vibrational spectroscopy. At room temperature most molecules exist in their ground vibrational states and in order to excite them to higher vibrational states energy must be absorbed. The two experimental techniques which are used to detect changes in vibrational energy states are infrared spectroscopy (IR) and Raman spectroscopy. Although both spectroscopic methods are concerned with vibrations in molecules, they differ in the manner in which interaction with the exciting radiation occurs. It is not the intention to present a comprehensive treatment of the basic theory of vibrational spectroscopy so the interested reader is advised to consult more detailed texts [3,4]. 5.11 INFRARED SPECTROSCOPY When molecular vibrations result in a change in the bond dipole moment, as a consequence of change in the electron distribution in the bond, it is possible to stimulate transitions between energy levels by interaction with EM radiation of an appropriate frequency. When the vibrating dipole is in phase with the electric vector of the incident radiation the vibrations are enhanced and there is transfer of energy from the incident radiation to the m