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Titolo:
HOLE, ELECTRON AND ENERGY-TRANSFER THROUGH BRIDGED SYSTEMS .8. SOLITON MOLECULAR SWITCHING IN SYMMETRY-BROKEN BROOKER (POLYMETHINECYANINE) CATIONS
Autore:
REIMERS JR; HUSH NS;
Indirizzi:
UNIV SYDNEY,DEPT PHYS & THEORET CHEM SYDNEY NSW 2006 AUSTRALIA UNIV SYDNEY,DEPT BIOCHEM SYDNEY NSW 2006 AUSTRALIA
Titolo Testata:
Chemical physics
fascicolo: 2-3, volume: 176, anno: 1993,
pagine: 407 - 420
SICI:
0301-0104(1993)176:2-3<407:HEAETB>2.0.ZU;2-E
Fonte:
ISI
Lingua:
ENG
Soggetto:
NEGATIVE-DEFECT TRANSPOLYACETYLENE; MODEL COMPOUNDS; BIS(PENTAAMMINERUTHENIUM) COMPLEXES; FINITE-LENGTH; POLYENES; POLARIZABILITIES; POLYACETYLENE; SPECTROSCOPY; TRANS-(CH)X; POLYMERS;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Citazioni:
61
Recensione:
Indirizzi per estratti:
Citazione:
J.R. Reimers e N.S. Hush, "HOLE, ELECTRON AND ENERGY-TRANSFER THROUGH BRIDGED SYSTEMS .8. SOLITON MOLECULAR SWITCHING IN SYMMETRY-BROKEN BROOKER (POLYMETHINECYANINE) CATIONS", Chemical physics, 176(2-3), 1993, pp. 407-420

Abstract

Brooker ions NH2-(CH)2n+1-NH2+ and their derivatives are extremely important dye and photosensitizer materials, and, if the inner odd-polyene chain length can be made sufficiently large, they will display the interesting conductivity properties of polyacetylene derivatives. Theycould be useful as molecular wires, with the conductivity actually exceeding that of finite-length doped polyacetylene until Peierls distortion sets in and solitons form. We explore the possibility, predicted by AM 1 calculations, that, at sufficiently large chain lengths, solitons form and are attracted to localized structures near the chain endsrather than forming a symmetric (C2v) Structure. While non-linear optical responses of the symmetrical Brooker ions are known to be alreadyvery large, calculations predict order of magnitude improvements in these properties upon localization. Also, the appearance of a new far-infrared intervalence-type transition is predicted. The isomerization reaction which interconverts the localized soliton structures is a holetransfer process the passage of the soliton carrying with it the net ionic charge. Details of the kinetics are considered, including their modulation by external electric fields and neighbouring charges, and estimates of the electronic coupling of the diabatic surfaces and of the reorganization energy are made. This suggests that, for Brooker ionswith optimal properties, a molecular switch could be constructed withsubpicosecond write times and at least microsecond data retention times. The kinetics of this type of switch are fundamentally different from those of other systems which have been considered as possible molecular switches.

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Documento generato il 24/11/20 alle ore 22:28:39