Ab initio calculations of hydrogen transfers. A computational test of variations in the transition-state structure and the coefficient of rate-equilibrium correlation

1988 ◽  
Vol 53 (14) ◽  
pp. 3232-3238 ◽  
Author(s):  
Hiroshi Yamataka ◽  
Shigeru Nagase
Keyword(s):  
Transition State ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
State Structure ◽  
Transition State Structure ◽  
Equilibrium Correlation

Nitro–Nitrite Isomerization and Transition State Switching in the Dissociation of Ionized Nitromethane: A Threshold Photoelectron–Photoion Coincidence Spectroscopy Study

2009 ◽  
Vol 15 (2) ◽  
pp. 157-166 ◽  
Author(s):  
Brandon Ferrier ◽  
Anne-Marie Boulanger ◽  
David M.P. Holland ◽  
David A. Shaw ◽  
Paul M. Mayer
Keyword(s):  
Transition State ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Bond Cleavage ◽  
Cleavage Reaction ◽  
Nitrite Ion ◽  
Methyl Nitrite ◽  
Bond Cleavage Reaction ◽  
Entropy Of Activation ◽  
Lower Entropy

Threshold photoelectron–photoion coincidence (TPEPICO) spectroscopy has been employed to investigate the competition between bond cleavage and rearrangement reactions in the dissociation of ionized nitromethane, 1. Modeling TPEPICO breakdown diagrams with a combination of RRKM theory and ab initio calculations at the G3 level of theory allowed the derivation of the activation energy for the isomerisation of 1 to ionized methyl nitrite, 2, 82 kJ mol−1. In addition, evidence was found for a transition state switch in the bond cleavage reaction in 1 leading to CH3• + NO2+. As internal energy increases, the effective transition state for this reaction becomes tighter (i.e. is characterized by a lower entropy of activation, Δ‡S). Fitted thresholds for NO+ and CH2OHO+ ions, originating from the isomeric methyl nitrite ion, are consistent with G3 level ab initio calculations.

Rearrangement of chorismate to prephenate. Use of chorismate mutase inhibitors to define the transition state structure

Biochemistry ◽  
1977 ◽  
Vol 16 (22) ◽  
pp. 4848-4852 ◽  
Author(s):  
P. R. Andrews ◽  
E. N. Cain ◽  
E. Rizzardo ◽  
G. D. Smith
Keyword(s):  
Transition State ◽  
Chorismate Mutase ◽  
State Structure ◽  
Transition State Structure

Conservation of Transition State Structure in Fast Folding Peripheral Subunit-Binding Domains

2008 ◽  
Vol 383 (1) ◽  
pp. 224-237 ◽  
Author(s):  
Timothy D. Sharpe ◽  
Neil Ferguson ◽  
Christopher M. Johnson ◽  
Alan R. Fersht
Keyword(s):  
Transition State ◽  
State Structure ◽  
Transition State Structure ◽  
Binding Domains
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