Absorption spectra bands

Shida and Hamill23 found that the positive and negative molecular ions of 1,3-butadiene and its homologs have similar absorption spectra. Band maxima of the anions are not sensitive to substituent alkyl groups, whereas those of the cations are red-shifted as the number of substituent methyl groups increases. In alcoholic matrices the butadiene anions abstract the alcoholic proton to form an allylic radical (equation 23), as was proven by ESR spectroscopy. 

The nitro group is a chromophore. In the visible and ultraviolet absorption spectra bands it (bonding)(anti-bonding) and n (non-bonding)— w occur most frequently in conjugated molecules including aromatics 1 -7). 

Equation (B 1.1.8) gives the intensity of one vibronic band in an absorption spectrum. It is also of interest to consider... 

A different example of non-adiabatic effects is found in the absorption spectrum of pyrazine [171,172]. In this spectrum, the, Si state is a weak structured band, whereas the S2 state is an intense broad, fairly featureless band. Importantly, the fluorescence lifetime is seen fo dramatically decrease in fhe energy region of the 82 band. There is thus an efficient nonradiative relaxation path from this state, which results in the broad spectrum. Again, this is due to vibronic coupling between the two states [109,173,174]. 

Information about the structure of a molecule can frequently be obtained from observations of its absorption spectrum. The positions of the absorption bands due to any molecule depend upon its atomic and electronic configuration. To a first approximation, the internal energy E oi a, molecule can be regarded as composed of additive contributions from the electronic motions within the molecule (Et), the vibrational motions of the constituent atoms relative to one another E ), and the rotational motion of the molecule as a whole (Ef) ... 

The ultraviolet absorption spectrum of thiazole was first determined in 1955 in ethanolic solution by Leandri et al. (172), then in 1957 by Sheinker et al. (173), and in 1967 by Coltbourne et al. (174). Albert in 1957 gave the spectrum in aqueous solution at pH 5 and in acidic solution (NHCl) (175). Nonhydroxylic solvents were employed (176, 177), and the vapor-phase spectrum was also determined (123). The results summarized in Table 1-15 are homogeneous except for the first data of Leandri (172). Both bands A and B have a red shift of about 3 nm when thiazole is dissolved in hydrocarbon solvents. This red shift of band A increases when the solvent is hydroxylic and, in the case of water, especially when the solution becomes acidic and the extinction coefficient increases simultaneously. 

Figure 9.18 shows a typical energy level diagram of a dye molecule including the lowest electronic states Sq, and S2 in the singlet manifold and and T2 in the triplet manifold. Associated with each of these states are vibrational and rotational sub-levels broadened to such an extent in the liquid that they form a continuum. As a result the absorption spectrum, such as that in Figure 9.17, is typical of a liquid phase spectrum showing almost no structure within the band system. 

Figure 9.32 Isotopic enrichment of SFg by multiphoton dissociation following irradiation in the vibrational band of SFg. The absorption spectrum is shown (a) before and (b) after irradiation. (Reproduced, with permission, from Letokhov, V S., Nature, Land., Ill, 605, 1979 Copyright 1979 Macmillan Journals Limited)...

Figure 9.37 Cavity ring-down absorption spectrum of O2, showing part of the 1-0 band of the system. (Reproduced, with permission, from O Keefe, A. and Deacon, D. A. G., Rev. Sci. Instrumen., 59, 2544, 1988)...

Figure 9.39 Cavity ring-down absorption spectrum showing (below) the 0-0 band of the A n /2-...

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)...

Electronic transitions in molecules in supersonic jets may be investigated by intersecting the jet with a tunable dye laser in the region of molecular flow and observing the total fluorescence intensity. As the laser is tuned across the absorption band system a fluorescence excitation spectrum results which strongly resembles the absorption spectrum. The spectrum... 

In Modulation Spectroscopy, which is mosdy used to characterize semiconductor materials, the peak positions, intensities and widths of features in the absorption spectrum are monitored. The positions, particularly the band edge (which defines the band gap)> are the most useful, allowing determination of alloy concentration. 

RAIRS spectra contain absorption band structures related to electronic transitions and vibrations of the bulk, the surface, or adsorbed molecules. In reflectance spectroscopy the ahsorhance is usually determined hy calculating -log(Rs/Ro), where Rs represents the reflectance from the adsorhate-covered substrate and Rq is the reflectance from the bare substrate. For thin films with strong dipole oscillators, the Berre-man effect, which can lead to an additional feature in the reflectance spectrum, must also be considered (Sect. 4.9 Ellipsometry). The frequencies, intensities, full widths at half maximum, and band line-shapes in the absorption spectrum yield information about adsorption states, chemical environment, ordering effects, and vibrational coupling. 

Many other measures of solvent polarity have been developed. One of the most useful is based on shifts in the absorption spectrum of a reference dye. The positions of absorption bands are, in general, sensitive to solvent polarity because the electronic distribution, and therefore the polarity, of the excited state is different from that of the ground state. The shift in the absorption maximum reflects the effect of solvent on the energy gap between the ground-state and excited-state molecules. An empirical solvent polarity measure called y(30) is based on this concept. Some values of this measure for common solvents are given in Table 4.12 along with the dielectric constants for the solvents. It can be seen that there is a rather different order of polarity given by these two quantities. 

The UV absorption spectrum of benzoisotellurazole is similar to those of its sulfur and selenium analogues, all absorption bands of the former being bathochromi-cally shifted relative to the latter compounds. The NMR signal of the H-3 proton... 

In the process of inhibition polypyrocatechin borate interacts with polyethylene macroradicals to form the B—O—C bonds. This is confirmed by the fact that the absorption spectrum of polyethylene inhibited with polypyrocatechin borate revealed the bands in the region of 1350 cm" characteristic for the B—O—C bond. There is no such a band in the spectrum of pure polypyrocatechin borate after heating under the same conditions. Chemical analysis of boron in polyethylene provides support for the IR-spectroscopy data concerning the presence of chemically bonded boron in polyethylene after destruction. 

Table 27. IR absorption spectrum and band assignment of Nb02F43 (D4h) in the compound K.2NaNb02F4 (F - occurs in tran -position relative to the oxygen ion). Reproduced from [195], K. Dehnike, G. Pausewang, W. Rudorff, Z. Anorg. Allg. Chem. 366 (1969) 64, Copyright 1969, with permission of Wiley-VCH.

IR absorption spectrum of the initial tantalum-saturated solution displays a weak band at about 880 cm 1, which corresponds to TaO bonds. The formation of the oxyfluorotantalate complex seems to be similar to the formation of oxyfluoroniobate in a niobium-saturated solution, but in the case of tantalum, the above effect is more emphasized. 

A quick analysis of Equation (77) shows that if the melt layer is thin (kd 1), the emission spectrum corresponds to an absorption spectrum. This means that the emission peaks occur at the same wave numbers as the absorption bands. In case of thick melt layers (kd 1) Equation (77) becomes the following expression ... 

Figure 16-36 shows the absorption spectra of thin films of four differently substituted five-ring OPVs. in contrast to the solution spectra, which show structureless low-energy absorption bands, the absorption bands of the films are structured. In the solid slate, the molecules are spatially constrained, whereas in solution different conformers exist, resulting in a distribution of accessible levels. As a consequence, some details appear in the absorption spectrum of the films which can be attributed to vibronic coupling, while, in dilute solution, the spectrum is a broad featureless band. For oct-OPV5 and Ooci-OPV5 films, the absorption maxima are red-shifted over approximately 0.1 eV relative to the solution (see Fig. 16-12). The low-energy absorption band of a thin film of Ooct-OPV5-CN" displays an appreciably larger...

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