Harmonic oscillators bound motion

Figure 5-2 Synchronous and Antisynchronous Modes of Motion in a Bound, Two-Mass Harmonic Oscillator.

The vibrational and rotational motions of the chemically bound constituents of matter have frequencies in the IR region. Industrial IR spectroscopy is concerned primarily with molecular vibrations, as transitions between individual rotational states can be measured only in IR spectra of small molecules in the gas phase. Rotational - vibrational transitions are analysed by quantum mechanics. To a first approximation, the vibrational frequency of a bond in the mid-IR can be treated as a simple harmonic oscillator by the following equation ... 

Figure 3.1 Energy levels and wave functions of harmonic oscillator. Heavy line bounding potential (3.2). Light solid lines quantum-mechanic probability density distributions for various quantum vibrational numbers see section 1.16.1). Dashed lines classical probability distribution maximum classical probability is observed in the zone of inversion of motion where velocity is zero. From McMillan (1985). Reprinted with permission of The Mineralogical Society of America.

Weakly bound complexes display unusual structural and dynamical properties resulting from the shape of their intermolecular potential energy surfaces. They show large amplitude internal motions, and do not conform to the dynamics and selection rules based on the harmonic oscillator/rigid rotor models (4). Consequently, conventional models used in the analysis of the spectroscopic data fail, and the knowledge of the full intermolecular potential and dipole/polarizability surfaces is essential to determine the assignments of the observed transitions. 

The classical theory of absorption in dielectric materials is due to H. A. Lorentz and in metals it is the result of the work of P. K. L. Drude. Both models treat the optically active electrons in a material as classical oscillators. In the Lorentz model the electron is considered to be bound to the nucleus by a harmonic restoring force. In this manner, Lorentz s picture is that of the nonconductive dielectric. Drude considered the electrons to be free and set the restoring force in the Lorentz model equal to zero. Both models include a damping term in the electron s equation of motion which in more modem terms is recognized as a result of electron-phonon collisions. 

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