Extinction coefficient of absorption

The decrease of molar extinction coefficients of absorption bands in the polarized spectra of piemontites with increasing Mn3+ ion contents ( 4.4.2), which is contrary to the Beer-Lambert law, eq. (3.7), indicates that Mn3+ ions are not located entirely in one site of the epidote structure ( 4.4.2.1). Most of the man-... 

The butyl derivative of these nickel complexes was investigated as a dye in a guest-host system using 4-pentyl-4 -cyanobiphenyl (5CB) as the host. The complex was found to have a large extinction coefficient of absorption (e = 28,000 moC dm cm at 860 nm) and dissolved in 5CB at concentrations up to 10% (w/w). At 20 °C, such solutions showed a dichroic ratio (Rd. defined as + /+x = absorbance) of 4.97 and a dye order parameter of 0.57. 

The cis-trans isomerization of stilbenes is technically another photochromic reaction (18). Although the absorption bands of the stilbene isomers, occur at nearly identical wavelengths, the extinction coefficient of the lowest energy band of cis-stilbene [645-49-8] is generally less than that of stilbene [103-30-0],... 

When 1, 3, 3-triethoxypropene was hydrolyzed with IN sulfuric acid, a solution of malonaldehyde whose optical density was perfectly stable at 350 m/x for at least one week was obtained. If the solution was made alkaline, the optical density at the same wavelength increased by a small value and then remained virtually constant for at least one week (56). It was also observed that in these solutions the extinction coefficient at 350 m/x was very low (observed 8.3, 61.5 and 69, for solutions of pH 0.4, 7.15 and 9.4 respectively) compared with previously reported values which varied from 200 ( 40) to 1000 ( 48). On the other hand, the absorption of solutions having a pH of 3 to 5, increased considerably with time (at pH 4.75, the extinction coefficient of malonaldehyde at 350 m/x was initially about 40 after four weeks a value of about 930 was recorded and the optical density of the solution was still increasing). This increase in absorption was accompanied by a marked decrease in the malonaldehyde content of the solution, as measured by the thiobarbituric acid method. As a corollary, it was found that aqueous solutions of malonaldehyde, prepared by autocatalyzed hydrolysis (33) of the same acetal and which had a pH of about 3.5, showed, at the completion of the hydrolysis, considerably higher extinction coefficient values at 350 m/x than did those malonaldehyde solutions which were prepared by hydrolysis with IN acid and subsequently adjusted to pH 4. It appears, therefore, that at pH values at which most of the periodate oxidations are carried out, malonaldehyde is unstable and undergoes a chemical reaction, the nature of which is not, as yet, known. 

These observations provide at least one explanation for the fact that variable results are obtained when malonaldehyde is oxidized with periodate. They also explain why widely differing values for the extinction coefficient of malonaldehyde at 350 m/x have been reported and make it unlikely that the absorption band at this wavelength is caused by the dialdehydo form of malonaldehyde. 

The reduced symmetry of the chromophore, which still contains 187t-electrons and is therefore an aromatic system, influences the electronic spectrum which shows a bathochromic shift and a higher molar extinction coefficient of the long-wavelength absorption bands compared to the porphyrin, so that the photophysical properties of the chlorins resulting from this structural alteration render them naturally suitable as pigments for photosynthesis and also make them of interest in medical applications, e.g. photodynamic tumor therapy (PDT).2... 

Billmers and Smith recorded the UV-Vis absorption spectra of sulfur vapor at various pressures (9-320 Torr or 1.2-42.7 kPa) and temperatures (670-900 K) but failed in obtaining the correct reaction enthalpy for the interconversion of S3 and S4 from the absorption intensities [19]. The molar extinction coefficient of S3 at 400 nm exceeds that of S4 at 520 nm by more than one order of magnitude. While the S3 absorption band at 360-440 nm exhibits a vibrational fine structme, the two broad S4 absorption bands at... 

The extinction coefficients of carotenoids have been listed completely bnt solvent effects can shift the absorption patterns. If a colorant molecnle is transferred into a more polar environment, then the absorption will be snbjected to a bathochro-mic (red) shift. If the colorant molecnle is transferred into a more apolar enviromnent, the absorption will be subjected to a hypsochromic (blue) shift. If a carotenoid molecule is transferred from a hexane or ethanol solution into a chloroform solution, the bathochromic shift will be 10 to 20 nm. 

As was discussed in the previous part, the temperature elevation in the solutions can be ascribed to the absorption of the NIR light by the solvents. In order to quantitatively explain the temperature elevation coefficient, AT/AP, for other solvents, we proposed a simple model that can parametrize the temperature elevation. As easily predicted, the AT/AP value is closely related to the extinction coefficient of light absorption, a, and the thermal conductivity, X. Heat generated at the focal point ofthe NIR beam is proportional to the extinction coefficient, a, and the incident laser power, P, as represented by Eq. (8.5). 

No new absorption bands are observed in other cases, largely due to the fact that the strong absorptions of the aromatic donors obstruct the UV-spectral measurements. For the complex between CBr4 and TMPD, the quantitative analyses of the temperature and concentration-dependent absorptions of the new band at 380 nm afford the extinction coefficient of ct = 3.2 x 103 M 1 cm x, as well as the thermodynamic parameters for complex formation AH = - 4.5 kcalM x, AS = - 14 e.u., and Kda = 0.3 M x at 295 K. Such thermodynamic characteristics are similar to those of the dihalogen complexes of as well as those of other acceptors with aromatic donors. Similar results are also obtained for CBr4 associates with halide and thio-cyanide anions [5,53]. 

Details of the ultraviolet absorption maxima for simple silenes, silaaro-matics, and for some relatively stable silenes are known and have been summarized.6 The simplest silenes absorb in the region 245-260 nm, with unknown extinction coefficients but as the substituents become increasingly complex, the Xmax values of the silenes increase until, with the silene (Me3Si)2Si=C(OSiMe3)Ad, the absorption occurs at 340 nm5 with an extinction coefficient of about 7400, consistent with a tt-it transition. A few further studies of interest are summarized below. 

Compounds containing doubly bonded tin are highly colored due to a strong absorption in the visible spectrum (77-77 transition of the double bond). The extinction coefficients of the distannene [[(Me3Si)2CH]2Sn]2 (entry 3, Table VII) were found to depend on concentration and temperature5 that for the absorption at 332 nm increases with dilution while that for the 495 nm absorption decreases. This suggests that the absorptions arise from two different species, presumably the distannene and the stannylene. By comparison with the other absorption maxima of doubly bonded tin compounds, the absorption at 495 nm is probably that of the distannene. 

The experimental findings of the optical density in the absorption region of the C=0 group (1770 cm-1 at a layer thickness of h = 0.87 x 10 4 cm), of the molar extinction coefficients of irradiated and non-irradiated copolymer films, and of the intensities of absorbed light (= 405 nm) made it possible to determine the quantum efficiency of C=0 group consumption using the known equation... 

Hence the quantity of EA can be simply calculated from the corrected sensitized emission image and the acceptor only image provided the ratio of the molar extinction coefficients of the donor and acceptor at the donor excitation wavelength is known (ct). This quantity can be determined from absorption spectra of purified labeled components or can be experimentally determined as follows. First, let us define a factor v that relates the signal of N acceptors in the S channel to the signal of the same number of donors in the D channel ... 

The major applications of the OTTLE cell are (i) to obtain spectra of electrogenerated species and thence to obtain the extinction coefficients of its major absorption bands, and (ii) to determine the standard redox potential of a reversible couple. The latter experiment relies on the thin-layer electrochemical characteristics of the cell. Thus, for the couple ... 

Before in situ external reflectance FTIR can be employed quantitatively to the study of near-electrode processes, one final experimental problem must be overcome the determination of the thickness of the thin layer between electrode and window. This is a fundamental aspect of the application of this increasingly important technique, marking an obstacle that must be overcome if it is to attain its true potential, due to the dearth of extinction coefficients in the IR available in the literature. In the study of adsorbed species this determination is unimportant, as the extinction coefficients of the absorption bands of the surface species can be determined via coulometry. 

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