Nature of the Excitons

At this point, it is necessary to distinguish between two types of excitons Frenkel excitons and Wannier-Mott excitons, because the nature of the exciton is closely related to their propagation mechanism. 

Anderson, and Warman have investigated the polarizability of two different covalently bridged porphyrin oligomers by flash photolysis time-resolved microwave conductivity measurements. When the bridge forbids electronic interactions, only electrostatic interactions are present and the excitation generates Frenkel-type excitons. Upon photoexcitation, only a slight increase of polarizability is observed ( 20 A ). When electronic communication is permitted by 

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Fig. 11.6 Scheme illustrating various transfer processes from the host to the guest electron (hole) transfer from the host LUMO (HOMO) to the guest LUMO (HOMO), Forster-type energy transfer between singlet states and Dexter-type energy transfer from the host to the guest triplet state. The nature of the excitonic state is simplified for better clarity. 

The nature of the light emissions is influenced by the way in which the absorbed energy is transferred through the polymer matrix. In crystalline polymers, exciton migration is possible as all molecules lose their energetic individuality and all electronic and oscillation levels are coupled [20]. Thus, new exciton absorption and emission bands are formed and the excitation energy can move along the chain ... 

The small and weakly time-dependent CPG that persisLs at longer delays can be explained by the slower diffusion of excitons approaching the localization edge [15]. An alternative and intriguing explanation is, however, field-induced on-chain dissociation, a process that does not depend on the local environment but on the nature of the intrachain state. The one-dimensional Wannier exciton model describes the excited state [44]. Dissociation occurs because the electric field reduces the Coulomb barrier, thus enhancing the escape probability. This picture is interesting, but so far we do not have any clear proof of its validity. 

Measurements of the optical properties in this range of wavelengths can probe the fundamental electronic transitions in these nanostructures. Some of the aforementioned effects have in fact been experimentally revealed in this series of experiments (90). As mentioned above, the IF nanoparticles in this study were prepared by a careful sulfidization of oxide nanoparticles. Briefly, the reaction starts on the surface of the oxide nanoparticle and proceeds inward, and hence the number of closed (fullerene-like) sulfide layers can be controlled quite accurately during the reaction. Also, the deeper the sulfide layer in the nanoparticle, the smaller is its radius and the larger is the strain in the nanostructure. Once available in sufficient quantities, the absorption spectra of thin films of the fullerene-like particles and nanotubes were measured at various temperatures (4-300 K). The excitonic nature of the absorption of the nanoparticles was established, which is a manifestation of the semiconducting nature of the material. Furthermore, a clear red shift in the ex-citon energy, which increased with the number of sulfide layers of the nanoparticles, was also observed (see Fig. 21). The temperature dependence of the exciton... 

In the present work the Cl procedure ( ) employed includes single, double, and higher excited configurations, and can treat in a natural way, using the localized monomer basis orbitals, intra- as well as inter-molecular excitations. States which arise from such monomer-based excitations can then be interpreted in terms of their locally-excited, excitonic, CT, or "mixed" character. Details as to the nature of the dimer states have been discussed in our earlier works (7, 8). 

We mentioned the main models for generation, transfer, and recombination of the charge carriers in polymers. Very often, these models are interwoven. For example, the photogeneration can be considered in the frame of the exciton model and transport in the frame of the hopping one. The concrete nature of the impurity centers, deep and shallow traps, intermediate neutral and charged states are specific for different types of polymers. We will try to take into account these perculiarities for different classes of the macro-molecules materials in the next sections. 

Many authors have investigated the photoconductivity of the polydiacetylenes [142-171], The main problem discussed concerns the nature of the initial act of the photoeffect. At first, most authors considered the exciton formation to occur at the beginning with consequent dissociation on the free carriers. Then it was shown the broad band existence for directions along the chains. The unification of the excitonic and band model of the free charge carrier generation was developed [146-150],... 

Movement of an electron from the ground electronic state of a molecule to an excited state creates a momentary dipole, called an electric transition dipole. Thus, associated with each electric transition is a polarization (electric transition dipole moment) that has both direction and intensity which vary according to the nature of the chromophore and the particular excitation. When two or more chromophores lie sufficiently close together, their electric transition dipoles may interact through dipole-dipole (or exciton) coupling. Exciton coupling arises from the interaction of two (or more) chromophores through... 

D McBranch, MB Sinclair. Ultrafast photoinduced absorption in nondegenerate ground-state conjugated polymers Signatures of excited states. In NS Sariciftci, ed. Nature of the Photoexcitations in Conjugated Polymers Semiconductor Band vs. Exciton Model, New York World Scientific, 1997. 

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