Regions visible

The most extensive studies in the visible region were made by Kistia-kowsky (51) at a mean wavelength of about 6200 A. These experiments and other unpublished experiments of Kistiakowsky were considered by Schumacher (70), and a satisfactory mechanism was proposed. Following reaction (24) the simplest subsequent reactions are  

The maximum quantum yield possible would be two, and using the absorbed light intensity, Ia, as the rate of formation of O atoms in reaction (24), the rate expression is 

This rate expression was found to fit the results particularly well at low concentrations of ozone in mixtures with high concentrations of oxygen. The order of effectiveness of various gases for inhibition of the decomposition of ozone was found to be O2, 1 C02, 0.8 N2, 0.3 He, 0.13. Making allowance for the fact that 02 may be a reactant in reaction (27) as well 

Some quantum yields of greater than two but less than three have been reported by Schumacher (71) for the unpublished data of Kistia-kowsky. Benson (13), however, has pointed out that the error in the quantum yield determination makes the value about 30% uncertain, and, therefore, there is no acceptable evidence that quantum yields in this wavelength region may exceed two. A chain mechanism is then not necessary to explain the results. 

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One of the well known advantages of resonance Raman spectroscopy is that samples dissolved in water can be studied since water is transparent in the visible region. Furthennore, many molecules of biophysical interest assume their native state in water. For this reason, resonance Raman spectroscopy has been particularly strongly embraced in the biophysical connnunity. 

The resolution of the Raman spectrum is detemiined by the monoclnomator. Furthennore, since the light bemg measured is in the visible region, usually around 20 000 cnc the resolution of the monoclnomator must be significantly better than that of its IR counterpart because the resolving power is described by Av/v. That is, for... 

Chance B 1951 Rapid and sensitive spectrophotometry. I. The accelerated and stopped-flow methods for the measurement of the reaction kinetics and spectra of unstable compounds in the visible region of the spectrum Rev. Sci. Instrum 22 619-27... 

Another interesting physical feature relates to the cliromophoric character of fullerenes. Based on the symmetry prohibitions, solutions of [60]fullerene absorb predominantly in the UV region, with distinct maxima at 220, 260 and 330 nm. In contrast to extinction coefficients on the order of 10 cm at these wavelengths, the visible region shows only relatively weak transitions (X at 536 nm s =710 cm ) [142]. 

A dye molecule has one or more absorption bands in the visible region of the electromagnetic spectrum (approximately 350-700 nm). After absorbing photons, the electronically excited molecules transfer to a more stable (triplet) state, which eventually emits photons (fluoresces) at a longer wavelength (composing three-level system.) The delay allows an inverted population to build up. Sometimes there are more than three levels. For example, the europium complex (Figure 18.15) has a four-level system. 

Until the advent of lasers the most intense monochromatic sources available were atomic emission sources from which an intense, discrete line in the visible or near-ultraviolet region was isolated by optical filtering if necessary. The most often used source of this kind was the mercury discharge lamp operating at the vapour pressure of mercury. Three of the most intense lines are at 253.7 nm (near-ultraviolet), 404.7 nm and 435.7 nm (both in the visible region). Although the line width is typically small the narrowest has a width of about 0.2 cm, which places a limit on the resolution which can be achieved. 

Whereas the emission spectrum of the hydrogen atom shows only one series, the Balmer series (see Figure 1.1), in the visible region the alkali metals show at least three. The spectra can be excited in a discharge lamp containing a sample of the appropriate metal. One series was called the principal series because it could also be observed in absorption through a column of the vapour. The other two were called sharp and diffuse because of their general appearance. A part of a fourth series, called the fundamental series, can sometimes be observed. 

Flowever, transition metal complexes do absorb in the visible region, giving them a characteristic colour. Flow can this happen if the transitions are forbidden The answer is that interaction may occur between the motion of the electrons and vibrational motions so that some vibronic transitions are allowed (see Section 7.3.4.2b). 

A diode, or semiconductor, laser operates in the near-infrared and into the visible region of the spectmm. Like the mby and Nd YAG lasers it is a solid state laser but the mechanism involved is quite different. 

One characteristic property of dyes is their colour due to absorption from the ground electronic state Sq to the first excited singlet state Sj lying in the visible region. Also typical of a dye is a high absorbing power characterized by a value of the oscillator strength/ (see Equation 2.18) close to 1, and also a value of the fluorescence quantum yield (see Equation 7.135) close to 1. 

One of the first applications of this technique was to the enrichment of and "B isotopes, present as 18.7 and 81.3 per cent, respectively, in natural abundance. Boron trichloride, BCI3, dissociates when irradiated with a pulsed CO2 laser in the 3g vibrational band at 958 cm (vj is an e vibration of the planar, D j, molecule). One of the products of dissociation was detected by reaction with O2 to form BO which then produced chemiluminescence (emission of radiation as a result of energy gained by chemical reaction) in the visible region due to A U — fluorescence. Irradiation in the 3g band of BCls or "BCI3 resulted in °BO or BO chemiluminescence. The fluorescence of °BO is easily resolved from that of "BO. 

Multiple-Bubble Sonoluminescence. The sonoluminescence of aqueous solutions has been often examined over the past thirty years. The spectmm of MBSL in water consists of a peak at 310 nm and a broad continuum throughout the visible region. An intensive study of aqueous MBSL was conducted by VerraH and Sehgal (35). The emission at 310 nm is from excited-state OH, but the continuum is difficult to interpret. MBSL from aqueous and alcohol solutions of many metal salts have been reported and are characterized by emission from metal atom excited states (36). 

Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy. Attenuated total redectance (atr) ftir spectroscopy is based on the principle of total internal redection (40). Methods based on internal redection in the uv and visible regions of the spectmm are also common in addition to those in the ir region. The implementation of internal redection in the ir region of the spectmm provides a means of obtaining ir spectra of surfaces or interfaces, thus providing moleculady-specific vibrational information. 

Hydantoin derivatives show weak absorption in the uv-visible region, unless a part of the molecule other than the imidazohdinedione ring behaves as a chromophore (13) however, piC values have been determined by spectrophotometry in favorable cases (14). Absorption of uvby thiohydantoins is more intense, and the two bands observed have been attributed to n — tt and n — tr transitions of the thiocarbonyl group (15,16). Several piC values of thiohydantoins have been determined by uv-visible spectrophotometry (16). 

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