A modified two-sphere model for solvent reorganization energy in electron transfer

2012 ◽  
Vol 14 (16) ◽  
pp. 5538 ◽  
Author(s):  
Han-Yu Wu ◽  
Hai-Sheng Ren ◽  
Quan Zhu ◽  
Xiang-Yuan Li
Keyword(s):  
Electron Transfer ◽  
Reorganization Energy ◽  
Sphere Model ◽  
Solvent Reorganization Energy

SOLVENT REORGANIZATION ENERGY WITH DIELECTRIC GREEN FUNCTIONAL AND ITS APPLICATION TO RETURN ELECTRON TRANSFER IN TETRACYANOETHYLENE-HEXAMETHYLBENZENE SYSTEM

2004 ◽  
Vol 03 (04) ◽  
pp. 609-627 ◽  
Author(s):  
QUAN ZHU ◽  
KE-XIANG FU ◽  
XIANG-YUAN LI ◽  
JI-FENG LIU
Keyword(s):  
Electron Transfer ◽  
Free Energy ◽  
Reorganization Energy ◽  
Energy Difference ◽  
Solute Molecule ◽  
Sphere Model ◽  
Free Energy Difference ◽  
Solvent Reorganization Energy ◽  
Electrostatic Free Energy ◽  
Non Equilibrium

Based on classical electrodynamics, the proper integral formula for general cases is adopted to estimate the electrostatic free energy difference between two given states, e.g. equilibrium and non-equilibrium states in the charging process of solute molecule in solution. With adequate consideration of the change of dielectric property in establishing the non-equilibrium state, the electrostatic free energy for this state can be obtained in a form differing from the traditional theories. The general formula of the solvent reorganization energy is derived according to the definition of the free energy difference between the non-equilibrium and equilibrium states due to the same electronic state of the solute molecule. Applying it to the two-sphere model and single-sphere model, we obtain the new expressions of the solvent reorganization energy, which are convenient to be used in practice. In the investigation of the return electron transfer of tetracyanoethylene-hexmethylbenzene system, good results can be obtained by using our expression when they are compared with those from the experiment.

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