Electronic transitions exhibited

Given some notion of the nature of the endogenous ligands, we can next ask how exogenous ligands perturb the copper atom and what this can tell us about the electronic transitions exhibited by the Cu(II) atom in galactose oxidase. 

Table II. Electronic Transitions Exhibited by Galactose Oxidase"...

Fig. 39. Excitation profiles (solid curves) and depolarization dispersion curves (broken curves) of a nontotally symmetric fundamental (

TD-DFT is a mono-determinantal method, and thus it cannot be applied to electronic states with an intrinsic multireference character [2]. Analogously, TD-DFT can exhibit deficiencies in treating electronic transitions with substantial contributions from double excitations [63-66], although interesting attempts to overcome the above limitations have been proposed [65-71]. In several cases, however, an electronic transition exhibits a multireference character (or a significant contribution from double excitations) just because of a poor description of the ground-state MO by HF orbitals, and such features are not present when using MOs computed at the DFT level. 

The PL spectrum and onset of the absorption spectrum of poly(2,5-dioctyloxy-para-phenylene vinylene) (DOO-PPV) are shown in Figure 7-8b. The PL spectrum exhibits several phonon replica at 1.8, 1.98, and 2.15 eV. The PL spectrum is not corrected for the system spectral response or self-absorption. These corrections would affect the relative intensities of the peaks, but not their positions. The highest energy peak is taken as the zero-phonon (0-0) transition and the two lower peaks correspond to one- and two-phonon transitions (1-0 and 2-0, respectively). The 2-0 transition is significantly broader than the 0-0 transition. This could be explained by the existence of several unresolved phonon modes which couple to electronic transitions. In this section we concentrate on films and dilute solutions of DOO-PPV, though similar measurements have been carried out on MEH-PPV [23]. Fresh DOO-PPV thin films were cast from chloroform solutions of 5% molar concentration onto quartz substrates the films were kept under constant vacuum. 

However, while transition-metal ions often contain unpaired electrons, they exhibit none of the reactivity that is commonly associated with such radicals outside the d block. There is no behaviour comparable to that of the highly reactive and short lived radicals such as CH3. Also associated with the presence of unpaired electrons in these species is the phenomenon of paramagnetism. The long-term stability of many compounds with unpaired electrons is a characteristic of the transition-metal series. 

Although the n-n and tz-tz electronic transitions of the urea chromophore have not been studied as extensively as amides, the contribution of the backbone is expected to dominate the far UV spectra of oligoureas in a fashion similar to that which is observed for peptides. The CD spectra recorded in MeOH of oligoureas 177 and 178 show an intense maximum near 204 nm (Figure 2.48). This is in contrast to helical y" -peptides that do not exhibit any characteristic CD signature. 

Compounds having the same optical configuration show similar Cotton effects. If the absolute configuration is known (for example, from x-ray diffraction) for one optically active compound, a similar Cotton effect exhibited by another compound indicates that it has the same optical configuration as the known. In other words, if two compounds give electronic transitions that show Cotton effects that... 

Thiazyl monomer is a radical with one unpaired electron. It exhibits an IR band at 1209 cm-1. The experimental dipole moment is 1.83 0.03 D in the opposite direction to that in NO (p = 0.16 D). Much less is known about selenazyl monomer, SeN, but it has been characterized by infrared spectroscopy.36 The structure of a transition-metal complex [OsTp(NSe)Cl2] (Tp=hydrotris(l-pyr-azolyl)borate) has been determined.39... 

The light reflected by a powdered solid will consist of a specular reflection component and of a diffuse reflection component. The specular component represents reflection of the incident light by the surfaces of the component particles, and it is characterized by a complete absence of light transmission through the interiors of the particles. By contrast, diffuse reflectance is associated with the radiation that penetrates into the particles to some extent and that then emerges from the bulk solid. This light will exhibit spectral characteristics that are modified from those of the incident beam by the electronic transitions that took place within the solid phase and at the boundaries of the component particles. 

A molecule exhibits a great difference in the speeds of electronic transitions and vibrational atomic motions. The absorbtion of photon and a change in the electronic state of a molecule occurs in 10 15—10—18 s. The vibrational motion of atoms in a molecule takes place in 10 1 s. Therefore, an electronically excited molecule has the interatomic configuration of the nonexited state during some period of time. Different situations for the exited molecule can exist. Each situation is governed by the Franck-Condon principle [203,204],... 

As for the homopolymers, dilute solution (1 x 10-4 M in toluene, isooctane or THF) spectroscopic studies were carried out over the temperature range of —70 to +80°C. The CD spectrum of 54 (Figure 4.39), containing 50% p-(S)-2-methylbutylphenyl-substituted monomer units, exhibits a positively signed Cotton effect (389 nm), almost coincident with the lowest energy main-chain electronic transition (or-or ) in the 20°C UV spectrum (394 nm). The CD spectra of 53 and 55 show similar features to that of 54, and the similarity... 

The data shows that the high coverage partially oxidized polymer exhibits new absorptions at 2fi and at 0.8/x, while the low coverage polymer only has a new absorption at 0.8/i, with no electronic transitions observed at lower energy. In contrast to this the monomeric species, oxidized under the same conditions, shows no electronic absorptions in this region throughout the complete range (0-100%) of donor oxidation. 

The phthalocyanines, naphthalocyanines, and certain of their metal derivatives (Figure 6.17) are infrared fluorophores. 61"64 As a class, they are exceptionally stable compounds, with copper (Cu) phthalocyanine (not a fluorophore) remaining intact above 300 °C in air. First used for textile dyeing in the last century and still widely used, there is a rich chemistry of phthalocyanines. Most derivatives can be made by prolonged heating of a phthalimide or phthalic acid derivative with a metal in powder or salt form at elevated temperature. Several derivatives absorb in the near-IR, and either fluoresce or phosphoresce. The electronic transitions of phthalocyanines are complex and have been extensively studied, at least in part because the symmetry of the molecule makes theoretical calculations of its spectroscopic behavior more tractable. Unsubstituted phthalocyanines and naphthalocyanines are, as a class, very insoluble in solvents other than, for instance, nitrobenzene. Sulfonated phthalocyanines are water soluble and exhibit spectra comparable to the parent derivative. Photolumines-cent phthalocyanines (Pcs) include SiPc, ZnPc, and PC itself. These compounds have been little used for practical infrared fluorometry to date however, Diatron Corpora-... 

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