Combination absorption bands

These cross-terms have the effect of reducing the actual frequency of combination absorption bands in exactly the same way as overtone bands, even though only excitation to n = 1 levels are involved. 

Dominant near-infrared spectral features include the measurement of the overtones and combination absorption bands from the following functional groups. The table and composite spectra further define the locations of these groups in typical NIR spectra. 

Molecular vibration absorptions are typically observed at infrared wavelengths, which correspond to the resonance frequencies for fundamental molecular vibrations. Because of the molecular potential anharmonicity, however, overtone and combination absorption bands also appear at visible and near-infrared wavelengths. The predominant factor for attenuation in POFs has been the stretching overtone absorptions of C-H bonds. 

Photoexcited fluorescence from spread monolayers may be studied [158,159] if the substance has both a strong absorption band and a high emission yield as in the case for chlorophyll [159]. Gaines and co-workers [160] have reported on the emission from monolayers of Ru(bipyridine)3, one of the pyridine ligands having attached C g aliphatic chains. Ruorescence depolarization provides information about the restriction of rotational diffusion of molecules in a monolayer [161], Combining pressure-area... 

Appreciable interaction between chromophores does not occur unless they are linked directly to each other, or forced into close proximity as a result of molecular stereochemical configuration. Interposition of a single methylene group, or meta orientation about an aromatic ring, is sufficient to insulate chromophores almost completely from each other. Certain combinations of functional groups afford chromophoric systems which give rise to characteristic absorption bands. 

A powerful characteristic of RAIR spectroscopy is that the technique can be used to determine the orientation of surface species. The reason for this is as follows. When parallel polarized infrared radiation is specularly reflected off of a substrate at a large angle of incidence, the incident and reflected waves combine to form a standing wave that has its electric field vector (E) perpendicular to the substrate surface. Since the intensity of an infrared absorption band is proportional to / ( M), where M is the transition moment , it can be seen that the intensity of a band is maximum when E and M are parallel (i.e., both perpendicular to the surface). / is a minimum when M is parallel to the surface (as stated above, E is always perpendicular to the surface in RAIR spectroscopy). 

In this article we have reviewed the results of a joint spectroscopic and morphological investigation of -sexilhienyl (T(J. The lowest singlet electronic level, which is assigned to I B , splits in the single crystal into four crystalline levels. The structure of the exciton band is investigated by the combined absorption and... 

The oscillator strength of the longest wavelength absorption band of BMPC (1.1, [25]) is very similar to those of two previously studied carbocyanines (DOC and DTC) [45] so that we can expect that, for BMPC as well as for EK)C and DTC, the radiative constant (kp) is equal to 2-3x10 s". Combining this value with the fluorescence quantum yield of BMPC in methanol, 4)p= 5.3x10", we can estimate its room-temperarnre fluorescence lifetime to be = 2 ps. 

This result is further supported by the very short 130 + 10 ps lifetime combined with the remarkably high quantum yield of 0.43, both observed upon excitation at 335 nm, near the long-wavelength edge of the absorption band. These values combine to a radiative lifetime of 300 ps, which corresponds (33a) to an oscillator strength of 1.8. Similarly short emission lifetimes have been observed for other poly(di-n-alkylsilanes) di-n-pentyl, 200 ps, di-n-decyl, 150 ps. The average oscillator... 

Valence Band Spectroscopy. Optical and electronic properties of UPD metal flms on metal electrodes have been studied in situ by means of differential- and electroreflectance spectroscopy [98], Optical absorption bands, however, reflect a combined density of electronic states at a photon energy which is the energetic difference of... 

Absorption of ultraviolet and visible radiation in organic molecules is restricted to certain functional groups (chromophores) that contain valence electrons of low excitation energy (Figure 4). The spectrum of a molecule containing these chromophores is complex. This is because the superposition of rotational and vibrational transitions on the electronic transitions gives a combination of overlapping lines. This appears as a continuous absorption band. 

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). 

The utilization of IR spectroscopy is very important in the characterization of pseudopolymorphic systems, especially hydrates. It has been used to study the pseudopolymorphic systems SQ-33600 [36], mefloquine hydrochloride [37], ranitidine HC1 [38], carbovir [39], and paroxetine hydrochloride [40]. In the case of SQ-33600 [36], humidity-dependent changes in the crystal properties of the disodium salt of this new HMG-CoA reductase inhibitor were characterized by a combination of physical analytical techniques. Three crystalline solid hydrates were identified, each having a definite stability over a range of humidity. Diffuse reflectance IR spectra were acquired on SQ-33600 material exposed to different relative humidity (RH) conditions. A sharp absorption band at 3640 cm-1 was indicative of the OH stretching mode associated with either strongly bound or crystalline water (Fig. 5A). The sharpness of the band is evidence of a bound species even at the lowest levels of moisture content. The bound nature of this water contained in low-moisture samples was confirmed by variable-temperature (VT) diffuse reflectance studies. As shown in Fig. 5B, the 3640 cm-1 peak progressively decreased in intensity upon thermal... 

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%). 

In the cyclophane 1, although the overlap between the n-system (2p) and the bridging cr-bonds (2s2p) is most effective, these orbital energy levels match worst, the first ionization potentials being 9.25 eV for benzene and 12.1 eV for ethane. As a result, the HOMOs are the almost pure it MOs with the b2g and b3g combinations. Both the PE spectrum and theoretical calculation demonstrate the degeneracy of the two HOMO levels. The absorption bands are attributed to the 17-17 transitions associated with the HOMOs. 

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