scholarly journals Competition between excited state proton and OH− transport via a short water wire: solvent effects open the gate

2014 ◽  
Vol 16 (26) ◽  
pp. 13047-13051 ◽  
Author(s):  
Gül Bekçioğlu ◽  
Christoph Allolio ◽  
Maria Ekimova ◽  
Erik T. J. Nibbering ◽  
Daniel Sebastiani
Keyword(s):  
Excited State ◽  
Exchange Reaction ◽  
Quantum Chemical Calculations ◽  
Solvent Effects ◽  
Quantum Chemical ◽  
Proton Exchange ◽  
Acid Base

We investigate the acid–base proton exchange reaction in a microsolvated bifunctional chromophore by means of quantum chemical calculations.

scholarly journals Proton exchange between oxymethyl radical and acids and bases: semiempirical quantum-chemical study

2016 ◽  
pp. 22-32
Author(s):  
Irina Pustolaikina ◽  
Kamshat Kutzhanova ◽  
Irina Stadnik ◽  
Alfia Kurmanova
Keyword(s):  
Hydrogen Bonding ◽  
Exchange Reaction ◽  
Carboxylic Acids ◽  
Quantum Chemical ◽  
Complex Structure ◽  
Quantum Chemical Study ◽  
Chemical Study ◽  
Proton Exchange ◽  
Exchange Mechanism ◽  
Acid Base

The reactions with proton participation are widely represented in the analytical, technological and biological chemistry. Quantum-chemical study of the exchange processes in hydrogen bonding complexes will allow us to achieve progress in the understanding of the elementary act mechanism of proton transfer in hydrogen bonding chain as well as the essence of the acid-base interactions. Oxymethyl radical •CH2ОН is small in size and comfortable as a model particle that well transmits protolytic properties of paramagnetic acids having more complex structure. Quantum-chemical modeling of proton exchange reaction oxymethyl radical ∙CH2OH and its diamagnetic analog CH3OH with amines, carboxylic acids and water was carried out using UAM1 method with the help of Gaussian-2009 program. QST2 method was used for the search of transition state, IRC procedure was applied for the calculation of descents along the reaction coordinate. The difference in the structure of transition states of ∙CH2OH/ CH3OH with bases and acids has been shown. It has been confirmed that in the case of bases, consecutive proton exchange mechanism was fixed, and in the case of complexes with carboxylic acids parallel proton exchange mechanism was fixed. The similarity in the reaction behavior of paramagnetic and diamagnetic systems in the proton exchange has been found. It was suggested that the mechanism of proton exchange reaction is determined by the structure of the hydrogen bonding cyclic complex, which is, in turn, depends from the nature of the acid-base interactions partners.

Identifiability of the Model of the Intermolecular Excited-State Proton Exchange Reaction in the Presence of pH Buffer

2004 ◽  
Vol 108 (40) ◽  
pp. 8180-8189 ◽  
Author(s):  
Noël Boens ◽  
Nikola Basarić ◽  
Eugene Novikov ◽  
Luis Crovetto ◽  
Angel Orte ◽  
...  
Keyword(s):  
Excited State ◽  
Exchange Reaction ◽  
Proton Exchange ◽  
Ph Buffer

Similarity between the kinetic parameters of the buffer-mediated proton exchange reaction of a xanthenic derivative in its ground- and excited-state

2010 ◽  
Vol 12 (2) ◽  
pp. 323-327 ◽  
Author(s):  
Jose M. Paredes ◽  
Angel Orte ◽  
Luis Crovetto ◽  
Jose M. Alvarez-Pez ◽  
Ramon Rios ◽  
...  
Keyword(s):  
Excited State ◽  
Kinetic Parameters ◽  
Exchange Reaction ◽  
Proton Exchange

scholarly journals Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge

2015 ◽  
Vol 13 (19) ◽  
pp. 5391-5398 ◽  
Author(s):  
Alexandra T. P. Carvalho ◽  
AnnMarie C. O'Donoghue ◽  
David R. W. Hodgson ◽  
Shina C. L. Kamerlin
Keyword(s):  
Quantum Chemical Calculations ◽  
Solvent Effects ◽  
Quantum Chemical ◽  
Hydrolysis Of ◽  
Role Of Solvent

Detailed quantum chemical calculations provide insight on the origin of large differences in experimental thio-effects for the hydrolysis of (thio)phosphodichloridates by water and hydroxide nucleophiles.

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