Combination band

Infrared Spectroscopy. The infrared spectroscopy of adsorbates has been studied for many years, especially for chemisorbed species (see Section XVIII-2C). In the case of physisorption, where the molecule remains intact, one is interested in how the molecular symmetry is altered on adsorption. Perhaps the conceptually simplest case is that of H2 on NaCl(lOO). Being homo-polar, Ha by itself has no allowed vibrational absorption (except for some weak collision-induced transitions) but when adsorbed, the reduced symmetry allows a vibrational spectrum to be observed. Fig. XVII-16 shows the infrared spectrum at 30 K for various degrees of monolayer coverage [96] (the adsorption is Langmuirian with half-coverage at about 10 atm). The bands labeled sf are for transitions of H2 on a smooth face and are from the 7 = 0 and J = 1 rotational states Q /fR) is assigned as a combination band. The bands labeled... 

Figure C 1.3.3. Comparison between infrared spectra for tire p bend combination band of Ar-HF obtained in tire gas phase and in a slit jet. (a) The gas-phase spectmm (Taken from 1361). (b) The slit jet spectmm (Taken from 1611).

Most infrared spectroscopy of complexes is carried out in tire mid-infrared, which is tire region in which tire monomers usually absorb infrared radiation. Van der Waals complexes can absorb mid-infrared radiation eitlier witli or without simultaneous excitation of intennolecular bending and stretching vibrations. The mid-infrared bands tliat contain tire most infonnation about intennolecular forces are combination bands, in which tire intennolecular vibrations are excited. Such spectra map out tire vibrational and rotational energy levels associated witli monomers in excited vibrational states and, tluis, provide infonnation on interaction potentials involving excited monomers, which may be slightly different from Arose for ground-state molecules. 

With broad-band pulses, pumping and probing processes become more complicated. With a broad-bandwidth pulse it is easy to drive fundamental and overtone transitions simultaneously, generating a complicated population distribution which depends on details of pulse stmcture [75], Broad-band probe pulses may be unable to distinguish between fundamental and overtone transitions. For example in IR-Raman experiments with broad-band probe pulses, excitation of the first overtone of a transition appears as a fundamental excitation with twice the intensity, and excitation of a combination band Q -t or appears as excitation of the two fundamentals 1761. 

These compounds have infrared spectra that are greatly complicated by harmonics and combination bands in the region of carbonyl group vibrations. 

A similar frequency shift is observed for their overtones or combination bands (204). It was also established that the proton-donating ability of the thiazole CH groups decreases in the order, 2>5>4 (204). 

The infrared and Raman spectra of many alkyl and arylthiazoles have been recorded. Band assignment and more fundamental work has been undertaken on a small number of derivatives. Several papers have been dedicated to the interpretation of infrared spectra (128-134, 860), but they are not always in agreement with each other. However, the work of Chouteau (99, 135) is noteworthy. The infrared spectrum of thiazole consists of 18 normal vibrations as well as harmonic and combination bands. 

The spectra of substituted thiazole derivatives, especially the methyl derivatives, can be used to determine harmonic and combination bands of the T(ch) modes 27(c.,h> T(c.hi + T[Pg.351]

Saturated 1725-1700 bands due to combination bands The monomer is near 1760 cm but is rarely... 

Figure 6.27 shows fhe f Sg infrared combination band of acefylene, where Vj is fhe symmefric CFI sfrefching vibration and Vj fhe cis bending vibration, as an example of a 77 — Zg band of a linear molecule. Nofe fhaf fhe P branch sfarts wifh P(2), rafher fhan / (f) as if would in a Z-Z fype of fransifion, and fhaf fhere is an intensify alternation of 1 3 for J"... 

Figure 9.40 Cavity ring-down absorption spectrum of HCN showing the overtone/combination band. (Reproduced, with permission, from Romanini, D. and Lehmann, K. K., J. Chem. Phys., 99, 6H1, 1993)...

The above, of course, is a very simplified picture, as many bands of much weaker intensities occur at shorter wavelengths (these are known as overtone bands and combination bands), but these are unlikely to be confused with the... 

The large number of modes in orthorhombic Ss results in a manifold of overtones and combination bands in the vibrational spectra [133]. As an ex-... 

The latter applies to NIR spectroscopy used for the non-invasive determination of blood glucose by means of a fibre-optical measuring-head (Jagemann et al. [1995] Muller et al. [1997] Danzer et al. [1998]). In addition to the weak overtone and combination bands resulting from glucose, strongly disturbing absorption of water, that is the main component... 

There is a strong water combination band in this region so the band could be related to this, but it shows potential-dependent behaviour and hence must be a surface species. 

The near-IR technique has been used very successfully for moisture determination, whole tablet assay, and blending validation [23]. These methods are typically easy to develop and validate, and far easier to run than more traditional assay methods. Using the overtone and combination bands of water, it was possible to develop near-IR methods whose accuracy was equivalent to that obtained using Karl-Fischer titration. The distinction among tablets of differing potencies could be performed very easily and, unlike HPLC methods, did not require destruction of the analyte materials to obtain a result. 

The number of fundamental vibrational modes of a molecule is equal to the number of degrees of vibrational freedom. For a nonlinear molecule of N atoms, 3N - 6 degrees of vibrational freedom exist. Hence, 3N - 6 fundamental vibrational modes. Six degrees of freedom are subtracted from a nonlinear molecule since (1) three coordinates are required to locate the molecule in space, and (2) an additional three coordinates are required to describe the orientation of the molecule based upon the three coordinates defining the position of the molecule in space. For a linear molecule, 3N - 5 fundamental vibrational modes are possible since only two degrees of rotational freedom exist. Thus, in a total vibrational analysis of a molecule by complementary IR and Raman techniques, 31V - 6 or 3N - 5 vibrational frequencies should be observed. It must be kept in mind that the fundamental modes of vibration of a molecule are described as transitions from one vibration state (energy level) to another (n = 1 in Eq. (2), Fig. 2). Sometimes, additional vibrational frequencies are detected in an IR and/or Raman spectrum. These additional absorption bands are due to forbidden transitions that occur and are described in the section on near-IR theory. Additionally, not all vibrational bands may be observed since some fundamental vibrations may be too weak to observe or give rise to overtone and/or combination bands (discussed later in the chapter). 

Near-infrared spectroscopy is quickly becoming a preferred technique for the quantitative identification of an active component within a formulated tablet. In addition, the same spectroscopic measurement can be used to determine water content since the combination band of water displays a fairly large absorption band in the near-IR. In one such study [41] the concentration of ceftazidime pentahydrate and water content in physical mixtures has been determined. Due to the ease of sample preparation, near-IR spectra were collected on 20 samples, and subsequent calibration curves were constructed for active ingredient and water content. An interesting aspect of this study was the determination that the calibration samples must be representative of the production process. When calibration curves were constructed from laboratory samples only, significant prediction errors were noted. When, however, calibration curves were constructed from laboratory and production samples, realistic prediction values were determined ( 5%). 

Another interesting facet of the vibrational IETS is the weakness of overtone and combination bands. There are sound theoretical reasons to expect that overtone bands should be very weak in IETS [46, 47]. To our knowledge, there has been no theoretical investigation of the intensities of combination bands in tunneling spectra. To be sure, there are experimental papers that contain tunneling band assignments that include assignments as combination and overtone bands. Most... 

Based on empirical observation, a general statement about overtones and combination bands might be Overtones do occur, but they are very weak. Combination bands are seldom observed. Kirtley, for example, says that overtones are about a factor of 200 weaker than fundamentals in the case of the benzoate ion [47, 53]. Ramsier, Henriksen, and Gent identify a single clear overtone in the tunneling spectrum of the phosphite ion (HPO3 2) [54], The fundamental associated with... 

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