Mechanisms of excitation transfer in multichromophoric systems
β Scribed by Gregory D. Scholes; Kenneth P. Ghiggino
- Publisher
- Elsevier Science
- Year
- 1994
- Tongue
- English
- Weight
- 740 KB
- Volume
- 80
- Category
- Article
- ISSN
- 1010-6030
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β¦ Synopsis
The nature of the interactions which promote interchromophore electronic excitation transfer are examined. They arc partitioned into direct and relayed components, where direct electronic coupling takes the form of a dipole-dipole interaction at large separations. Factors which modify this interaction at short to intermediate separations are discussed (with particular reference to aromatic polymer systems). The direct interaction is partitioned into coulombic, exchange and penetration terms; the significance of the penetration interaction at close separations (proposed recently for the first time) is elaborated upon here. The relayed interaction involves mediation of all these interactions over large direct separations via intervening moieties. It is demonstrated, using a model poly(acenaphthylene) dyad as an example, that relayed interactions, mediated via the ti bonds connecting two chromophores, are capable of increasing substantially the rate of electronic excitation transfer.
π SIMILAR VOLUMES
Steady-state fluorescence, lifetime measurements and time-resolved absorption spectra of the covalentty linked heterc dimers consisting of pheophorbide and porphyrin revealed rapid ( 1011-10'2 s-' ) and efficient singlet-singlet excitation energy transfer from porphyrin unit to pheophorbide.
The excited-state isomerization of 2-hydroxypyridine to 2( lH)-pyridone is considered as a model for UV photo-induced intramolecular hydrogen (or proton) transfer in systems without an intramolecular hydrogen bond. The potential energy functions of the electronic ground as well as of the lowest nn'