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Chapter 14:
Resonance Energy Transfer: Theoretical Foundations and Developing Applications
In the wide range of materials that are characterised by broad, relatively featureless optical spectra, the absorption of light in the ultraviolet-€”visible wavelength region is typically followed by rapid internal processes of dissipation and degradation of the acquired energy, the latter ultimately to be manifest in the form of heat. In more complex materials—those comprising a variety of light-absorbing atomic or molecular components (chromophores) with optically well characterised absorption and fluorescence bands—the absorption of light is commonly followed by a spatial translation of the absorbed electromagnetic radiation between different, though usually closely separated, chromophores. The process takes place well before the completion of any thermal degradation in such materials. This primary relocation of the acquired electronic energy, immediately following photo-excitation, is accomplished by a mechanism that has become known as resonance energy transfer (RET). (At an earlier stage in the development of these ideas, the term "€œresonance"€ was used to signify that no molecular vibrations were excited; however, such usage is now known to be relevant to few systems and has largely fallen into abeyance.) An alternative designation for the process is electronic energy transfer (EET); both terms are widely used, and in each case, the first letter of the acronym serves as a distinction from electron transfer. In complex multichromophore materials, the singular properties of RET allow the flow of energy to exhibit a directed character. Because the process operates most efficiently between near-neighbor chromophores, the resonance propagation of energy through such a system generally takes the form of a series of short steps; an alternative process involving fewer long steps proves considerably less favourable. In suitably designed materials, the pattern of energy flow following optical absorption is thus determined by a sequence of transfer steps, beginning and ending at chromophores that differ chemically, or, if the chromophores are structurally equivalent, through local modifications in energy level structure reflecting the influence of their electronic environment. Hence, individual chromophores that act in the capacity of excitation acceptors can subsequently adopt the role of donors. This effect contributes to a crucial, property-determining characteristic for the channeling of electronic excitation in photosynthetic systems; the same principles are emulated in synthetic energy harvesting systems such as the fractal polymers known as dendrimers.
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