Vibration spectra group frequencies

Polyatomic molecules vibrate in a very complicated way, but, expressed in temis of their normal coordinates, atoms or groups of atoms vibrate sinusoidally in phase, with the same frequency. Each mode of motion functions as an independent hamionic oscillator and, provided certain selection rules are satisfied, contributes a band to the vibrational spectr um. There will be at least as many bands as there are degrees of freedom, but the frequencies of the normal coordinates will dominate the vibrational spectrum for simple molecules. An example is water, which has a pair of infrared absorption maxima centered at about 3780 cm and a single peak at about 1580 cm (nist webbook). 

Despite the difficulty cited, the study of the vibrational spectrum of a liquid is useful to the extent that it is possible to separate intramolecular and inter-molecular modes of motion. It is now well established that the presence of disorder in a system can lead to localization of vibrational modes 28-34>, and that this localization is more pronounced the higher the vibrational frequency. It is also well established that there are low frequency coherent (phonon-like) excitations in a disordered material 35,36) These excitations are, however, heavily damped by virtue of the structural irregularities and the coupling between single molecule diffusive motion and collective motion of groups of atoms. 

Useful characteristic group frequency bands often involve coupled vibrations. The spectra of alcohols have a strong band in the region between 1260 and 1000 cm-1, which is usually designated as the C—O stretching band. In the spectrum of methanol this band... 

The complexity of the physical properties of liquid water is largely determined by the presence of a three-dimensional hydrogen bond (HB) network [1]. The HB s undergo continuous transformations that occur on ultrafast timescales. The molecular vibrations are especially sensitive to the presence of the HB network. For example, the spectrum of the OH-stretch vibrational mode is substantially broadened and shifted towards lower frequencies if the OH-group is involved in the HB. Therefore, the microscopic structure and the dynamics of water are expected to manifest themselves in the IR vibrational spectrum, and, therefore, can be studied by methods of ultrafast infrared spectroscopy. It has been shown in a number of ultrafast spectroscopic experiments and computer simulations that dephasing dynamics of the OH-stretch vibrations of water molecules in the liquid phase occurs on sub-picosecond timescales [2-14],... 

Such normal vibration analyses have been applied to the spectra of macromolecules to only a limited extent. In the first place, the only structure which has been analyzed in detail is that of the planar zig-zag chain of CHg groups, i.e., polyethylene. Neither substituted planar zig-zag chains nor the helical chain structures characteristic of many polymers [Bunn and Holmes (28)] have been submitted to such a theoretical analysis. In the second place, even for the case of polyethylene the answers are not in all instances unambiguous. Different assumptions as to the nature of the force field, and lack of knowledge of some of the force constants, has led to varying predictions of band positions in the observed spectrum. For the identification of certain modes, viz., those which retain the characteristics of separable group frequencies, such an analysis is not of primary importance, but for knowledge of skeletal frequencies and of interactions... 

P=0 Thomas and Chittenden (5,38 441 have carried out a thorough series of studies on the identification of organophosphorus compounds. The group frequency tables in these studies enable interpretation of many of the characteristic features in the spectra of nerve agents and related chemicals. Several structure-spectrum relationships give specific information on the molecule. One very valuable relation discovered by Thomas is the dependence of the position of the P=0 bond stretching vibration, vp=0, on the substituents on the phosphorus, represented by n constants ... 

The multiple nature of the M-CO bond increases the strength of the M-C bond and reduces the one of the C O bond, which can be observed in the vibrational spectrum of the metallic compound. The CO molecule has a stretching v(C-O) frequency of 2143 cm. When coordinated to a metal, the frequency is reduced to about 1900-2125 cm for terminal CO groups, showing a reduction in the CO bond order. Moreover, when changes are made to increase the extent of... 

When a molecule absorbs IR radiation, the molecular vibration with a frequency matching that of the radiation increases in amplitude. In other words, the spring connecting the two atoms stretches and compresses a bit further. Since each frequency absorbed by a molecule corresponds to a specific molecular motion, we can see what kinds of motions a molecule has by measuring its IR spectrum. By then interpreting those motions, we can find out what kinds of bonds (functional groups) are present in the molecule. 

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