Spectral region

Electrochromism, i.e. change of color or spectral signature with applied voltage (or equilibrium potential or chemical potential), is one of the most prominent and fundamental properties of CPs. It is one of those which aroused the most interest for practical applications initially. CPs possess the unique property that their color 

Other means to change chemical potential or redox equilibrium of a CP, and hence its color, include dilution in solvents (when the CPs are somewhat soluble) and change of temperature. These two effects, respectively Solvatochromism and Thermochromism, are treated elsewhere in this book. 

The change of color of a CP with doping is of course directly related to the creation of new, mid-gap states, and thus new optical transitions, as discussed at some length in Chapter 2. New absorptions, generally at higher wavelength (lower energy) are added to the customary valence conduction, (tt tt ), transition of the pristine, undoped CP. 

Electrochromism is observed not only in the Visible spectral region, but also in the near-UV (300 - 400 nm), near-IR (0.7 to 2.5 yim), mid IR (2.5 ptm to 8 yim), far-IR (8 fxm to 18 yim), and to some extent, microwave/mm-wave (5 MHz to 50 GHz) regions. Properly speaking, conductivity, including microwave conductivity, is also an electrochromic property, since it can be changed with applied potential or CP 

It is important to note that due to the nature of CP synthesis, usually involving presence of dopants, most freshly synthesized CPs and especially those prepared electrochemically, are not normally in their pristine (de-doped or virgin) state. Rather, these as-prepared CPs have a small doping level, of the order of 1% to 8%. 

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The study of small energy gaps in matter using the optical spectral region (say the near-IR, visible and UV) offers many advantages over direct one-photon spectroscopies in the IR, far IR or even the microwave. First,... 

Optical metiiods, in both bulb and beam expermrents, have been employed to detemiine tlie relative populations of individual internal quantum states of products of chemical reactions. Most connnonly, such methods employ a transition to an excited electronic, rather than vibrational, level of tlie molecule. Molecular electronic transitions occur in the visible and ultraviolet, and detection of emission in these spectral regions can be accomplished much more sensitively than in the infrared, where vibrational transitions occur. In addition to their use in the study of collisional reaction dynamics, laser spectroscopic methods have been widely applied for the measurement of temperature and species concentrations in many different kinds of reaction media, including combustion media [31] and atmospheric chemistry [32]. 

This teclnhque can be used both to pennit the spectroscopic detection of molecules, such as H2 and HCl, whose first electronic transition lies in the vacuum ultraviolet spectral region, for which laser excitation is possible but inconvenient [ ], or molecules such as CH that do not fluoresce. With 2-photon excitation, the required wavelengdis are in the ultraviolet, conveniently generated by frequency-doubled dye lasers, rather than 1-photon excitation in the vacuum ultraviolet. Figure B2.3.17 displays 2 + 1 REMPI spectra of the HCl and DCl products, both in their v = 0 vibrational levels, from the Cl + (CHg) CD reaction [ ]. For some electronic states of HCl/DCl, both parent and fragment ions are produced, and the spectrum in figure B2.3.17 for the DCl product was recorded by monitoring mass 2 (D ions. In this case, both isotopomers (D Cl and D Cl) are detected. 

The solvent chosen must dissolve the sample, yet be relatively transparent in the spectral region of interest. In order to avoid poor resolution and difficulties in spectrum interpretation, a solvent should not be employed for measurements that are near the wavelength of or are shorter than the wavelength of its ultraviolet cutoff, that is, the wavelength at which absorbance for the solvent alone approaches one absorbance unit. Ultraviolet cutoffs for solvents commonly used are given in Table 7.10. 

Transmission Fourier Transform Infrared Spectroscopy. The most straightforward method for the acquisition of in spectra of surface layers is standard transmission spectroscopy (35,36). This approach can only be used for samples which are partially in transparent or which can be diluted with an in transparent medium such as KBr and pressed into a transmissive pellet. The extent to which the in spectral region (typically ca 600 4000 cm ) is available for study depends on the in absorption characteristics of the soHd support material. Transmission ftir spectroscopy is most often used to study surface species on metal oxides. These soHds leave reasonably large spectral windows within which the spectral behavior of the surface species can be viewed. 

The detection of a specific gas (10) is accompHshed by comparing the signal of the detector that is constrained to the preselected spectral band pass with a reference detector having all conditions the same except that its preselected spectral band is not affected by the presence of the gas to be detected. Possible interference by other gases must be taken into account. It may be necessary to have multiple channels or spectral discrimination over an extended Spectral region to make identification highly probable. Except for covert surveillance most detection scenarios are highly controlled and identification is not too difficult. 

Interference effects, which arise because of the extraordinary uniformity of thickness of the film over the spectrometer sample beam, superimposed on the absorption of incident light by parylene films, can be observed. Experimentally, a sinusoidal undulation of the baseline of the spectmm is seen, particularly in the spectral regions where there is Htde absorption by the sample. These so-called "interference fringe" excursions can amount to some... 

The power density. A/, may be calculated using Plank s radiation law. For a 300 K scene temperature and the spectral region from 8 to 12 pm,... 

PMD color or the nature of the electron transitions produces the widest appHcation for PMDs. Depending on the polymethine chain length, the end-group topology, and the electron shell occupation, polymethines can absorb light in uv, visible, and near-ir spectral regions. 

The direction of the long-wavelength maximum shift caused by the heterosubstitution or the introduction of substituents is deterrnined by the Forster-Dewar-Knott rule (40—42). Spatial hindrances within the symmetrical PMDs cause bathochromic effects (39,43), whereas the introduction of an acetylenic bond is accompanied by the maximum shift to the short-wavelength spectral region (44). 

The reverse reaction, the photochemical ring opening of sphopyranes (22b), takes place by absorption ia the short-wave uv region of the spectmm and the merocyanine isomer (22a) is obtained. The electron transition of (22a) is ia the visible spectral region, whereas (22b) is colorless. As a result, the dye solution can change from colorless to a colored solution (87,88). These photochromic reactions can be used for technical appHcations (89). 

Spectral Sensitization. Photographic silver haHde emulsions ate active with light only up to about 500 nm. However, theh sensitivity can be extended within the whole visible and neat-H spectral region up to about 1200—1300 nm. This is reached by the addition of deeply colored dyes that transfer excited electrons or excitation energy to the silver haHde. 

Photopolymerization. In many cases polymerization is initiated by ittadiation of a sensitizer with ultraviolet or visible light. The excited state of the sensitizer may dissociate directiy to form active free radicals, or it may first undergo a bimoleculat electron-transfer reaction, the products of which initiate polymerization (14). TriphenylaLkylborate salts of polymethines such as (23) ate photoinitiators of free-radical polymerization. The sensitivity of these salts throughout the entire visible spectral region is the result of an intra-ion pair electron-transfer reaction (101). 

Instrumentation. The k region was developed usiag dispersive techniques adapted as appropriate from uv—vis spectroscopy. Unfortunately, k sources and detectors tend to be kiefficient compared to those for other spectral regions. 

A gamma-ray spectmm is produced nondispersively by pulse-height (multichannel) analysis using scintillation or semiconductor detectors. Resolving power, typically - 100 at 100 keV and - 700 at 2 MeV, is quite modest compared with that achievable in other spectral regions, but is sufficient to identify nucHdes unambiguously. 

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