Optical-absorption intermediates

Applications The differential optical absorption spectrometer has been used to monitor concentrations of gases or intermediate compounds such as SO, NO, O5, HCHO, HNO, CS, NO, and OH in the atmosphere.In atmospheric measurements with open paths of 100 to 1000 m, a detection limit of about 1 ppb can be achieved. In the emission measurements, the path length across the duct or the plume can range in meters. 

In the following sections, we first show the phonon dispersion relation of CNTs, and then the calculated results for the Raman intensity of a CNT are shown as a function of the polarisation direction. We also show the Raman calculation for a finite length of CNT, which is relevant to the intermediate frequency region. The enhancement of the Raman intensity is observed as a function of laser frequency when the laser excitation frequency is close to a frequency of high optical absorption, and this effect is called the resonant Raman effect. The observed Raman spectra of SWCNTs show resonant-Raman effects [5, 8], which will be given in the last section. 

One way to make the short-lived intermediates amenable to study is to increase their lifetime, usually by irradiating in the solid state and at very low temperatures. Then, the intermediates can be measured at the end of the irradiation by optical absorption spectroscopy or ESR. 

Whereas the intermediate existence of polarons has been unequivocally proved by ESR measurements and optical absorption data, up to now, the existent of bipolarons has been only indirectly deduced from the absence of the ESR signal and the disappearance of the visible polaron bands from the optical absorption spectrum On the other hand, spinfree — diionic-charge — states in aromatics, whose optical properties bear a remarkably resemblence to the predictions of the bipolaron model, have long been known Further evidence of bipolarons is the fact that doped... 

For example, the observed decreasing redox peaks in the cyclic voltammogram of Figure 10A is attributed to the consumption of the charged intermediates. The optical, absorption data of Figure 9 also appear to evidence bipolarons (dications) as intermediate and hence, consistent with this mechanism. 

One way to make the short-lived intermediates amenable to study is to increase their lifetime, usually by irradiation in the solid state and/or at very low temperatures. Then, the intermediates can be detected at the end of the irradiation by ESR or optical absorption spectroscopy. The ESR study of radicals in the solid state is done on single crystals, polycrystalline samples or frozen aqueous solution. In case of polycrystalline samples or frozen aqueous solution the identification of the radicals from the ESR spectra is difficult in many cases and, for better identification, the ESR experiment should be conducted on irradiated single crystals. Later, the method of spin trapping, developed for the liquid phase5, was extended to polycrystalline solids. In this technique the polycrystalline solids are /-irradiated and subsequently dissolved in a solution containing the spin trap. 

The subpicosecond pulse radiolysis [74,77] detects the optical absorption of short-lived intermediates in the time region of subpicoseconds by using a so-called stroboscopic technique as described in Sec. 10.2.2 ( History of Picosecond and Subpicosecosecond Pulse Radiolysis ). The short-lived intermediates produced in a sample by an electron pulse are detected by measuring the optical absorption using a very short probe light (a femtosecond laser in our system). The time profile of the optical absorption can be obtained by changing the delay between the electron pulse and the probe light. 

The life-time of the ionic intermediates in the liquid solutions is so short that it is difficult or impossible to observe them directly. One of the convenient ways to overcome this difficulty is to prolong the life-time by freezing the irradiated solution at low temperature. For convenience of measurement, organic substances frozen to a glassy state have been widely used as solvents for the study by means of optical absorption measurement at low temperature. A rigid glass matrix is preferably used also in the ESR study, because the experimental results are readily compared with those obtained by the optical study. 

One the other hand, short-lived intermediates formed from styrene by radiations were studied by the pulse radiolysis technique by Metz et al. (43). They observed the anion radicals of styrene as an optical absorption band with the maximum at 370 mp, but could not find cationic intermediates. Shida and Hillma irradiated the 2-methyltetrahydrofuran glass and butylchloride glass, both containing styrene, and observed the absorption bands due to added styrene at 410 mp and 350 mp, respectively. The former band was assumed to be due to the anion-radicals and the latter to the cation radicals (44). 

The 77-SCF MO Cl method has also been used446 to interpret spectral transitions of a series of possible intermediates in the reaction of uracil and cytosine with the solvated electrons eaq, produced by radiolysis of water. Experimentally this reaction has been investigated by Hayon,447 who used the technique of flash radiolysis. Hayon measured the optical-absorption spectra of the transient species in the UV range to obtain information on the site of attack of eaq on the pyrimidine base. At pH 5.0 the solvated electrons react with the pyrimidine molecules mainly at the C-2 and C-4 carbonyls, and the intermediates are rapidly protonatcd to give the corresponding ketyl radicals. For uracil Hayon found two absorption maxima (at 305 and < 280 nm) at pH 5.1 and one peak at 310 nm at pH 11.7. In this last case, on ionization of one of the chromophores the ketyl radical anion of the other nondissociated carbonyl is formed. Several species, 44, 45, 46, have been suggested by... 

Photochemical transformations of rhodopsin. The numbers in parentheses indicate the optical absorption maxima of the intermediates. The numbers in color on the right are approximate halftimes for the conversions in rod outer segment membranes near 37°... 

Rate studies of the reaction between cesium and water in ethylenediamine, using the stopped-flow technique, have been extended to all alkali metals. The earlier rate constant (k — 20 NT1 sec.-1) and, in some cases, a slower second-order process (k — 7 Af"1 sec.-1) have been observed. This is consistent with optical absorption data and agrees with recent results obtained in aqueous pulsed-radiolysis systems. Preliminary studies of the reaction rate of the solvated electron in ethylenediamine with other electron acceptors have been made. The rate constant for the reaction with ethylene-diammonium ions is about 105 NCl sec.-1 Reactions with methanol and with ethanol show rates similar to those with water. In addition, however, the presence of a strongly absorbing intermediate is indicated, which warrants more detailed examination. 

Hart and Boag s discovery (13) of the broad optical absorption band of the e aq in irradiated water confirmed the conclusion (7, 8) that the eaqy instead of the H atom, is the principal reducing intermediate in the bulk of the solution. Understandably, the Lea-Platzman (31) viewpoint of the primary physical processes of energy absorption gained currency over the Samuel-Magee (34) viewpoint. Their disagreement concerned the fate of the electron from primary ionization of water Platzman (31)... 

Hydroperoxo-ferric intermediate, termed also Compound 0, is the immediate precursor of the main catalytic intermediate Compound I in peroxidase enzymatic cycle. Attempts to study this intermediate directly in reactions of hydrogen peroxide with HRP using fast kinetic methods have been inconclusive, possibly because it is not accumulated in sufficient concentrations.90,91 However, Compound 0 could be prepared and studied by EPR and optical absorption spectroscopy via cryoreduction of... 

Optical absorption spectra of the hydroperoxo-ferric intermediate in HO64 show Soret maximum at 421 nm (5 nm red shifted as compared with 416 nm band for oxy-ferrous HO) and Q-bands at 530 and 557 nm. After annealing at 212-215 K, a new species is formed with Soret band at 406 nm characteristic for the o-meso-hydroxyheme. 

There are now good theoretical descriptions of the electronic structures contributing to the optical absorption bands in spectra of porphyrin radicals and ferryl species [160,167] most charge-transfer bands in the latter are due to a transition from a porphyrin p orbital to an Fe-0 tt orbital [167], However, in the absence of a prior knowledge of the structure around the Felv site (and/or spectra of a variety of synthetic model compounds) it is not straightforward to assign an optical spectrum to a ferryl species. Thus the intermediate assumed to be the ferryl species in the binuclear haem c /Cub centre of cytochrome c oxidase [168] has a spectrum at 580 nm essentially identical [169] to that of low-spin ferric haem a3 compounds (e.g. cyanide). 

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