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energy levels of given vibrations are the same; that is, a single absorption should appear for each vibration in which there is a change in dipole However, fewer experimental peaks may be observed than would be expected from the theoretical number of normal modes Fewer peaks can be found when the symmetry of the molecules is such that no change in dipole results from a particular vibration The energies of two or more vibrations can be identical or nearly identical In some cases absorption intensity is too low to be detected by ordinary means It may also happen that the vibrational energy is in a wavelength region which is beyond the range of the instrument Conversely, more peaks may be found than expected from the number of normal modes This is the typical situation that concerns the NIR domain.
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Overtone peaks at two or three times the frequency of a fundamental peak, or addition combination bands at approximately the sum or difference of two fundamental frequencies, are sometimes encountered The energy of a vibration and thus the wavelength of its absorption peak may be in uenced by, or coupled with, other vibrators in the molecule A number of factors in uence the extent of such coupling Vibration coupling is a common phenomenon As a result, the position of an absorption peak corresponding to a given organic functional group cannot always be speci ed exactly While interaction effects may lead to uncertainties in the identi cation of functional groups contained in a compound, it is this very effect that provides the unique features of an IR absorption spectrum that are so important for the positive identi cation of a speci c compound 422.
where U = ( x ~ > / ( x is ~ ratio of the expected noise to the expected > the signal power. Our second refinement is to take into account the fact that the fluctuation in the centroid position may not be regenerated independently from one turn to the next. In other words, if particles move rapidly from one sample to another, each sample will rerandomize during the course of one turn and we will have the ideal situation. But the mixing may not be perfect, and we have to allow for this possibility. The movement from sample to sample is due to the spread in orbital frequencies arising from the spread in particle momentum. The number of revolutions required for a particle of momentum A p / p to pass from one sample to another is
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