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Strong deviations from harmonic oscillator energies are found for levels indicated in brackets. These result from so-called Fermi resonances, or mixing of nearly resonant levels by anharmonic terms in the potential function. With data this extensive, it is 12 possible to deduce the potential function with great accuracy. Pariseau et al have found values fop all terms through those involving the fourth power of internal coordinates. -1 Fig. 2-3. Principle infrared a b s o r p t i o n re­ gions for the C 0 molecule (scale in c m 2 units).

Som e specifi c examples ma y hel p provid e som e insight . Th e symmetri c linea r triatomi c system i s almos t th e mos t comple x syste m whic h ca n easil y b e don e i n close d form. Let u s conside r a molecul e wit h th e structur e indicate d i n Fig . 2-1 . W e know tha t ther e ar e 3N — 5 = 4 interna l degree s o f freedom . Accordin g t o prescription, w e nee d t o choos e fou r interna l coordinate s s . I t i s reasonabl e to gues s tha t th e A—Β bond stretching motion and the Β — C stretching motion would be suitable.

Vibrational energy may also flow from one vibrational state to another (V-V energy transfer) with little energy flow into or out of translation and rotation. The experiments fall into roughly three categories. In the first category we might include spectroscopic experiments, that is, ones in which specific vibrational states are produced and in which specific vibrational states are monitored, usually through absorption and emission of electromagnetic radiation. These experiments have been generally carried out in systems at thermal equilibrium.

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