Search results for "transition state theory"
showing 4 items of 14 documents
Fission fragment angular distributions in the capture reactions 50Ti, 56Fe + 208Pb
2008
The analysis of %-ray mult ip l ic i t ies measured I in coincidence with capture fission events in reactions of 26Mg through 54Cr, 58Fe, and 64Ni with 208pb in terms of Ko and~eff revealed1 that the resulting values of ~ /~e f f were rather independent of for a given system and, in a compound nucleus picture, were more in agreement with the 'shape of the non-rotating saddle than with the actually expected rotating saddle I f non-compound systenmhave to be considered these values of ~/J~ff__ shapes. suggested at least that the captured systems near the turning point from the inward radial motion to symmetric fragmentation had reached a remarkable compactness.
A theoretical study on the decomposition mechanism of β-propiolactone and β-butyrolactone
1998
Abstract The reaction mechanism associated with the decomposition of β-propiolactone and β-butyrolactone in the gas phase to form carbon dioxide and ethylene or propene, respectively, has been theoretically characterized by using analytical gradients at the B3LYP/6-31G**, B3LYP/6-31++G**, MP2/6-31G** and MP2/6-31++G** calculation levels, as well as by single point calculations at QCISD(T)/6-31++G**//MP2/6-31++G**. A detailed analysis of the results points out that the reaction pathway can be described as an asynchronous concerted process. The geometrical parameters and the components of the transition vector are weakly dependent on the computational method. By applying transition state theo…
Are there dynamical effects in enzyme catalysis? Some thoughts concerning the enzymatic chemical step.
2015
Highlights • The possible role of enzymatic reaction dynamical effects is examined. • Solution reactions usefully inform the issue of dynamical effects in enzymes. • Division into regions containing and away from the transition state is important. • Motions in passage to/from the transition state need not lead to dynamical effects. • Transition State Theory is usually a reasonable description of enzyme kinetics.
Quantifying the limits of transition state theory in enzymatic catalysis
2017
Significance Transition state theory (TST) is the most popular theory to calculate the rates of enzymatic reactions. However, in some cases TST could fail due to the violation of the nonrecrossing hypothesis at the transition state. In the present work we show that even for one of the most controversial enzymatic reactions—the hydride transfer catalyzed by dihydrofolate reductase—the error associated to TST represents only a minor correction to the reaction rate. Moreover, this error is actually larger for the reaction in solution than in the enzymatic active site. Based on this finding and on previous studies we propose an “enzymatic shielding” hypothesis which encompasses various aspects …