The Visible Region

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). 

Radiation, both in the uv and in the visible region, can have a highly destmctive effect by decomposing the dye molecule. Other substances, particularly water, can reinforce the photochemical effect of light. Once the dyed material fades, its original condition usually cannot be restored. 

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