scholarly journals Crossover between the Adiabatic and Nonadiabatic Limits of Thermal Electron Transfer: Verifying the Landau-Zener Formula

2020 ◽  
Author(s):  
Guang Yuan Zhu ◽  
Yi Qin ◽  
Miao Meng ◽  
Suman Mallick ◽  
Hang Gao ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Transition Probability ◽  
Mixed Valence ◽  
Thermal Electron ◽  
Nonadiabatic Transition ◽  
Chemical Systems ◽  
Avoided Crossing ◽  
And Control ◽  
Thermal Electron Transfer ◽  
Theoretical Limitation

Abstract The semiclassical models of nonadiabatic transition were proposed first by Landau and Zener in 1932, which has been widely used in study of electron transfer (ET); however, experimental substantiation of the Landau-Zener formula remains challenging. Herein, employing the Marcus-Hush theory, thermal ET in mixed-valence complexes { [Mo2]-(ph)n-[Mo2] }+ (n = 1-3) is investigated and the Landau-Zener analysis performed in the adiabatic and nonadiabatic limits. Evidently, the Landau-Zener formula is valid in the adiabatic regime in a broader range of conditions than the theoretical limitation known as the narrow avoided-crossing. The intermediate system is identified with an overall transition probability (𝛋el) of ~ 0.5, which is resolved by the contributions from the single and the first multiple passage. The results unify the contemporary ET theories under the semiclassical framework. The obtained insights help to understand and control the ET processes in biological and chemical systems.

scholarly journals Crossover between the adiabatic and nonadiabatic electron transfer limits in the Landau-Zener model

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Guang Yuan Zhu ◽  
Yi Qin ◽  
Miao Meng ◽  
Suman Mallick ◽  
Hang Gao ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Transition Probability ◽  
Mixed Valence ◽  
Nonadiabatic Transition ◽  
Zener Model ◽  
Chemical Systems ◽  
Avoided Crossing ◽  
Nonadiabatic Electron Transfer ◽  
And Control ◽  
Theoretical Limitation

AbstractThe semiclassical models of nonadiabatic transition were proposed first by Landau and Zener in 1932, and have been widely used in the study of electron transfer (ET); however, experimental demonstration of the Landau-Zener formula remains challenging to observe. Herein, employing the Hush-Marcus theory, thermal ET in mixed-valence complexes {[Mo2]-(ph)n-[Mo2]}+ (n = 1–3) has been investigated, spanning the nonadiabatic throughout the adiabatic limit, by analysis of the intervalence transition absorbances. Evidently, the Landau-Zener formula is valid in the adiabatic regime in a broader range of conditions than the theoretical limitation known as the narrow avoided-crossing. The intermediate system is identified with an overall transition probability (κel) of ∼0.5, which is contributed by the single and the first multiple passage. This study shows that in the intermediate regime, the ET kinetic results derived from the adiabatic and nonadiabatic formalisms are nearly identical, in accordance with the Landau-Zener model. The obtained insights help to understand and control the ET processes in biological and chemical systems.

An Unusually Delocalized Mixed‐Valence State of a Cyanidometal‐Bridged Compound Induced by Thermal Electron Transfer

2017 ◽  
Vol 56 (6) ◽  
pp. 1605-1609 ◽  
Author(s):  
Xiao Ma ◽  
Chen‐Sheng Lin ◽  
Xiao‐Quan Zhu ◽  
Sheng‐Min Hu ◽  
Tian‐Lu Sheng ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Valence State ◽  
Mixed Valence ◽  
Thermal Electron ◽  
Mixed Valence State ◽  
Thermal Electron Transfer

An Unusually Delocalized Mixed-Valence State of a Cyanidometal-Bridged Compound Induced by Thermal Electron Transfer

2017 ◽  
Vol 129 (6) ◽  
pp. 1627-1631 ◽  
Author(s):  
Xiao Ma ◽  
Chen-Sheng Lin ◽  
Xiao-Quan Zhu ◽  
Sheng-Min Hu ◽  
Tian-Lu Sheng ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Valence State ◽  
Mixed Valence ◽  
Thermal Electron ◽  
Mixed Valence State ◽  
Thermal Electron Transfer

Optical and Thermal Electron Transfer Activation of Dioxygen by Viologen Dithiolene Metalates⊥

1997 ◽  
Vol 101 (37) ◽  
pp. 6876-6882 ◽  
Author(s):  
U. Ammon ◽  
C. Chiorboli ◽  
W. Dümler ◽  
G. Grampp ◽  
F. Scandola ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Thermal Electron ◽  
Thermal Electron Transfer

scholarly journals Перенос электрона между разнородными лантаноидами в кристаллах BaF-=SUB=-2-=/SUB=- --- II механизмы переноса

2019 ◽  
Vol 61 (5) ◽  
pp. 888
Author(s):  
Е.А. Раджабов ◽  
В.А. Козловский
Keyword(s):  
Electron Transfer ◽  
Low Temperatures ◽  
Barium Fluoride ◽  
Absorption Bands ◽  
Thermal Electron ◽  
Thermal Transfer ◽  
Trivalent Lanthanide ◽  
Fluoride Crystals ◽  
Divalent Lanthanide ◽  
Thermal Electron Transfer

The processes of electron transfer from a divalent lanthanide acceptor (Eu, Sm, Yb) to a trivalent lanthanide donor (Nd, Sm, Dy, Tm, Yb) and reverse thermal transfer are studied in barium fluoride crystals. Electron phototransfer at room temperatures is accompanied by a counter-movement of the charge-compensating interstitial fluorine. In the process of photobleaching at low temperatures, the divalent lanthanide donor turns out to be near the interstitial fluorine, which causes its 4f-5d absorption bands to shift to the red. The magnitude of the shift increases with decreasing size of the lanthanide in the series (Nd, Sm, Dy, Tm, Yb). Detailed mechanisms of photo and thermal electron transfer between heterogeneous lanthanides in BaF2 crystals are analyzed.

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