1987
DOI: 10.1063/1.453434
|View full text |Cite
|
Sign up to set email alerts
|

Outer sphere electron transfer in polar solvents. Activationless and inverted regimes

Abstract: In this paper we apply the stochastic Liouville equation for the study of outer sphere electron transfer (ET) in a polar solvent, which is characterized by a Debye dielectric relaxation. Explicit expressions, which bridge between the nonadiabatic and solvent-controlled adiabatic limits, are derived for the ET rates spanning a broad range of the energetic parameters, which include normal ET, activationless ET, and ET in the inverted region. The many-body result for the ET rate, which is accurate for symmetric E… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
3
1

Citation Types

1
77
0

Year Published

1990
1990
2012
2012

Publication Types

Select...
5
3
1

Relationship

0
9

Authors

Journals

citations
Cited by 169 publications
(78 citation statements)
references
References 23 publications
1
77
0
Order By: Relevance
“…For slow dielectric relaxation, the longitudinal relaxation time of the solvent, L, must be included as the solvent relaxation now happens on the same time scale as the reaction. This observation was first made by Kramers [75], who spoke of a solvent dynamic effect or solvent friction, and the theory was later expanded by authors like Zusman [76,77], Jortner and Rips [61,78,79], Marcus and Sumi [63] as well as several others.…”
mentioning
confidence: 98%
“…For slow dielectric relaxation, the longitudinal relaxation time of the solvent, L, must be included as the solvent relaxation now happens on the same time scale as the reaction. This observation was first made by Kramers [75], who spoke of a solvent dynamic effect or solvent friction, and the theory was later expanded by authors like Zusman [76,77], Jortner and Rips [61,78,79], Marcus and Sumi [63] as well as several others.…”
mentioning
confidence: 98%
“…Here a model of nonadiabatic coupling between LE and CT states is considered using Zusman-type kinetic equations. The corresponding steady-state rate coefficients in both systems can be evaluated in the Laplace space using the adiabaticity parameter Kj (0) or the time-scale functions f(x, y, 0) [21][22][23] where V,• is the electronic coupling parameter at the crossing point ci. For the case V, = V (symmetrical three-surface problem), j = 3, whereas for V = 0 and V,.…”
Section: (T) = (δQ(0)δq(t))/(δqmentioning
confidence: 99%
“…First, main theoretical concepts concerning the two [21][22][23] and three-surface [24][25][26] models of an electron transfer process in solution are given, subsequently the dependences of the time-scale functions [26][27][28] and the electron transfer rates in the two-surface model, as well as in the three-surface model, on the free energy for methanol, acetonitrile and water including the inertial effects are analyzed.…”
Section: Introductionmentioning
confidence: 99%
“…This is the so-called dynamic solvent effect ͑DSE͒ regime realizing at the highest friction. It was first studied in the Marcus normal region 8,[10][11][12][13][14][15] and opposed to the other regimes ͑of moderate and low friction͒ in a few reviews. 16,17 Later on the same analysis was done also for the Marcus inverted region where DSE takes place as well.…”
Section: Introductionmentioning
confidence: 99%