Proton Transfer in Nanoconfined Polar Solvents. 1. Free Energies and Solute Position

2005 ◽  
Vol 109 (11) ◽  
pp. 4941-4946 ◽  
Author(s):  
Shenmin Li ◽  
Ward H. Thompson
Keyword(s):  
Proton Transfer ◽  
Free Energies ◽  
Polar Solvents

Entropies and Free Energies of Protonation and Proton-Transfer Reactions

1997 ◽  
Vol 119 (38) ◽  
pp. 9014-9020 ◽  
Author(s):  
Allan L. L. East ◽  
Brian J. Smith ◽  
Leo Radom
Keyword(s):  
Proton Transfer ◽  
Transfer Reactions ◽  
Free Energies ◽  
Proton Transfer Reactions

Estimation of Surfactant Tail Transfer Free Energies from Polar Solvents to Micelle Core

Langmuir ◽  
1995 ◽  
Vol 11 (12) ◽  
pp. 4673-4677 ◽  
Author(s):  
R. Nagarajan ◽  
Chien-Chung Wang
Keyword(s):  
Free Energies ◽  
Polar Solvents ◽  
Micelle Core

scholarly journals Proton-Coupled Electron Transfer in the Reaction of 3,4-Dihydroxyphenylpyruvic Acid with Reactive Species in Various Media

2015 ◽  
Vol 2015 ◽  
pp. 1-13 ◽  
Author(s):  
J. J. Fifen ◽  
Z. Dhaouadi ◽  
M. Nsangou ◽  
O. Holtomo ◽  
N. Jaidane
Keyword(s):  
Electron Transfer ◽  
Proton Transfer ◽  
Activation Barrier ◽  
Bond Cleavage ◽  
Hydrogen Atom Transfer ◽  
Free Energies ◽  
Solvent Interactions ◽  
Proton Coupled Electron Transfer ◽  
Nonpolar Solvents ◽  
One Step

The distinction of concerted proton-coupled electron transfer (CPCET) from sequential one as well as proton transfer-electron transfer (PT-ET) from electron transfer-proton transfer (ET-PT) in the O–H bond cleavage reactions in various media has always been a difficult task. In this work, the activation barrier of the CPCET mechanism, its rate constants, and reaction free energies related to ET-PT and PT-ET involving coreactive species were presented as good parameters to attempt the problem. DFT calculations were carried out studying the described pathways subsequent to the scavenging of OH• and OBr- by the 3,4-DHPPA in various media. The solvation was described in a hybrid manner using IEF-PCM model conjointly with a model that takes into account some solute-solvent interactions. As a result, we found that the scavenging of hydroxyl radical by 3,4-DHPPA is thermodynamically governed by a one-step hydrogen atom transfer (CPCET) from the acid to the radical in all media. In kinetic viewpoint, CPCET still dominates in the vacuum and in nonpolar solvents, but in polar solvents it could compete strongly with the ET-PT mechanism so that the latter could slightly dominate.

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