Entropic driving-force effects upon preexponential factors for intramolecular electron transfer: implications for the assessment of nonadiabaticity

1984 ◽  
Vol 23 (2) ◽  
pp. 256-258 ◽  
Author(s):  
Joseph T. Hupp ◽  
Michael J. Weaver
Keyword(s):  
Electron Transfer ◽  
Driving Force ◽  
Intramolecular Electron Transfer

scholarly journals Solvatochromic and Ligand Effects in Ultrafast Intramolecular Electron Transfer in Fe-based Molecular Photosensitizers

2019 ◽  
Vol 205 ◽  
pp. 09029
Author(s):  
Kristjan Kunnus ◽  
Lin Li ◽  
Marco Reinhard ◽  
Sergey Koroidov ◽  
Kasper S. Kjaer ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Charge Transfer ◽  
Driving Force ◽  
Reorganization Energy ◽  
The Other ◽  
Intramolecular Electron Transfer ◽  
Ligand Effects ◽  
Ligand Charge Transfer ◽  
Excited State Lifetimes

Metal-to-ligand charge-transfer (MLCT) excited state lifetimes of [Fe(CN)4(2,2’-bipyridine)]2- and [Fe(CN)4(2,3-bis(2-pyridyl)pyrazine)]2-exhibit strong solvent and ligand dependence. We conclude that these effects can be described with Marcus-like model where changes in the MLCT energy correspond directly to the changes in the electron transfer driving force and all the other factors (e.g. reorganization energy) can be considered constant.

Long-lived charge-separated states of simple electron donor-acceptor dyads using porphyrins and phthalocyanines

2008 ◽  
Vol 12 (09) ◽  
pp. 993-1004 ◽  
Author(s):  
Kei Ohkubo ◽  
Shunichi Fukuzumi
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Electron Donor ◽  
Driving Force ◽  
Reorganization Energy ◽  
Charge Recombination ◽  
Zinc Phthalocyanine ◽  
Intramolecular Electron Transfer ◽  
Triplet Excited State ◽  
Donor Acceptor

Control of electron-transfer processes is described for a number of electron donor-acceptor dyads containing porphyrins or phthalocyanines as models for the photosynthetic reaction center. The rates for intramolecular electron transfer in the dyads are controlled by the driving force and reorganization energy of electron transfer. The small reorganization energy of electron transfer reactions and large driving force of charge recombination are required to form long-lived charge-separated states. A directly linked zinc chlorin-fullerene dyad, especially, has the longest lifetime of charge-separated state at 120 s at -150 °C, which is a much longer lifetime and higher energy than those of natural photosynthetic reaction centers. On the other hand, the charge-separated states of the phthalocyanine-based donor-acceptor dyads (silicon phthalocyanine-fullerene, and zinc phthalocyanine-perylenebisimide) are short-lived since charge recombination forms the low-lying triplet excited state of the chromophore. The energy of the charge-separated state of a zinc phthalocyanine-perylenebisimide dyad is decreased by binding of metal ions to the radical anion moiety in order to be lower than the triplet excited state. This results in formation of a long-lived charge-separated state. The mechanistic viability of formation of long-lived charge-separated states is demonstrated by a variety of examples based on the Marcus theory of electron transfer.

scholarly journals The effect of driving force on intramolecular electron transfer in proteins. Studies on single-site mutated azurins

1992 ◽  
Vol 210 (2) ◽  
pp. 399-403 ◽  
Author(s):  
Ole FARVER ◽  
Lars K. SKOV ◽  
Mart KAMP ◽  
Gerard W. CANTERS ◽  
Israel PECHT
Keyword(s):  
Electron Transfer ◽  
Driving Force ◽  
Single Site ◽  
Intramolecular Electron Transfer

Intramolecular Electron Transfer Mediated by a Tetrathiafulvalene Bridge in a Purely Organic Mixed-Valence System

2003 ◽  
Vol 42 (24) ◽  
pp. 2765-2768 ◽  
Author(s):  
Nicolas Gautier ◽  
Frédéric Dumur ◽  
Vega Lloveras ◽  
José Vidal-Gancedo ◽  
Jaume Veciana ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Mixed Valence ◽  
Intramolecular Electron Transfer
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