Intramolecular electron transfer in [4Fe-4S] proteins: estimates of the reorganization energy and electronic coupling in Chromatium vinosum ferredoxin

2001 ◽  
Vol 6 (4) ◽  
pp. 446-451 ◽  
Author(s):  
Rainer Kümmerle ◽  
Jacques Gaillard ◽  
Panayotis Kyritsis ◽  
Jean-Marc Moulis
Keyword(s):  
Electron Transfer ◽  
Reorganization Energy ◽  
Chromatium Vinosum ◽  
Electronic Coupling ◽  
Intramolecular Electron Transfer

Solvent Reorganization Energy and Electronic Coupling for Intramolecular Electron Transfer in Biphenyl-Acceptor Anion Radicals

2008 ◽  
Vol 21 (1) ◽  
pp. 45-54 ◽  
Author(s):  
Jing-bo Wang ◽  
Jian-yi Ma ◽  
Xiang-yuan Li ◽  
Fu-cheng He ◽  
Ke-xiang Fu
Keyword(s):  
Electron Transfer ◽  
Reorganization Energy ◽  
Electronic Coupling ◽  
Intramolecular Electron Transfer ◽  
Solvent Reorganization Energy ◽  
Anion Radicals

Small Reorganization Energy of Intramolecular Electron Transfer in Fullerene-Based Dyads with Short Linkage

2002 ◽  
Vol 106 (46) ◽  
pp. 10991-10998 ◽  
Author(s):  
Kei Ohkubo ◽  
Hiroshi Imahori ◽  
Jianguo Shao ◽  
Zhongping Ou ◽  
Karl M. Kadish ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Reorganization Energy ◽  
Intramolecular Electron Transfer

Photoinduced Intramolecular Electron Transfer and Electronic Coupling Interactions in π- Expanded Imidazole Derivatives

2014 ◽  
Vol 24 (5) ◽  
pp. 1379-1387
Author(s):  
J. Jayabharathi ◽  
V. Kalaiarasi ◽  
V. Thanikachalam ◽  
K. Vimal
Keyword(s):  
Electron Transfer ◽  
Electronic Coupling ◽  
Intramolecular Electron Transfer ◽  
Imidazole Derivatives

Preparation, characterization, and intramolecular electron transfer in pentaammineruthenium histidine-26 cytochrome b5 derivatives: role of the intervening medium in long-range donor-acceptor electronic coupling

1991 ◽  
Vol 113 (12) ◽  
pp. 4390-4394 ◽  
Author(s):  
Bradley A. Jacobs ◽  
Marcia R. Mauk ◽  
Walter D. Funk ◽  
Ross T. A. MacGillivray ◽  
A. Grant Mauk ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Long Range ◽  
Cytochrome B5 ◽  
Electronic Coupling ◽  
Intramolecular Electron Transfer ◽  
Donor Acceptor

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.

Intramolecular electron transfer in cyclopeptide involving tryptophan and tyrosine and corrected two-sphere model for solvent reorganization energy

2005 ◽  
Vol 312 (1-3) ◽  
pp. 21-29 ◽  
Author(s):  
Jin Tang ◽  
Xiang-Yuan Li ◽  
Ke-Xiang Fu ◽  
Ji-Feng Liu ◽  
Shen-Zhuang Lu
Keyword(s):  
Electron Transfer ◽  
Reorganization Energy ◽  
Intramolecular Electron Transfer ◽  
Sphere Model ◽  
Solvent Reorganization Energy

Electron transfer at the class II/III borderline of mixed valency: dependence of rates on solvent dynamics and observation of a localized-to-delocalized transition in freezing solvents

2007 ◽  
Vol 366 (1862) ◽  
pp. 177-185 ◽  
Author(s):  
Starla D Glover ◽  
Benjamin J Lear ◽  
J. Catherine Salsman ◽  
Casey H Londergan ◽  
Clifford P Kubiak
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Methylene Chloride ◽  
Mixed Valence ◽  
Reorganization Energy ◽  
Frequency Factor ◽  
Intramolecular Electron Transfer ◽  
Solvent Phase ◽  
Valence States ◽  
Solvent Dynamics

The dependence of the rates of intramolecular electron transfer (ET) of mixed-valence complexes of the type {[Ru 3 O(OAc) 6 (CO)(L)] 2 -BL} −1 , where L is the pyridyl ligand and BL is the pyrazine on solvent type and temperature is described. Complexes were reduced chemically to obtain the mixed-valence anions in acetonitrile (CH 3 CN) and methylene chloride (CH 2 Cl 2 ). Rate constants for intramolecular ET were estimated by simulating the observed degree of ν (CO) infrared (IR) bandshape coalescence in the mixed-valence state. In the strongly coupled mixed-valence states of these complexes, the electronic coupling, H AB , approaches λ /2, where λ is the total reorganization energy. The activation energy is thus nearly zero, and rate constants are in the ‘ultrafast’ regime where they depend on the pre-exponential terms within the frequency factor, ν N . The frequency factor contains both external (solvent dynamics) and internal (molecular vibrations) contributions. In general, external solvent motions are slower than internal vibrations, and therefore control ET rates in fluid solution. A profound increase in the degree of ν (CO) IR bandshape coalescence is observed as the temperature approaches the freezing points of the solvents methylene chloride (f.p. −92°C) and acetonitrile (f.p. −44°C). Decoupling the slower solvent motions involved in the frequency factor ν N for ET by freezing the solvent causes a transition from solvent dynamics to internal vibration-limited rates. The solvent phase transition causes a localized-to-delocalized transition in the mixed-valence ions that accelerates the rate of ET.

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.

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