Ensemble-averaged variation transition state

The SES, ESP, and NES methods are particularly well suited for use with continuum solvation models, but NES is not the only way to include nonequilibrium solvation. A method that has been very useful for enzyme kinetics with explicit solvent representations is ensemble-averaged variational transition state theory [26,27,87] (EA-VTST). In this method one divides the system into a primary subsystem and a secondary one. For an ensemble of configurations of the secondary subsystem, one calculates the MEP of the primary subsystem. Thus the reaction coordinate determined by the MEP depends on the coordinates of the secondary subsystem, and in this way the secondary subsystem participates in the reaction coordinate. 

Ensemble-averaged Variational Transition State Theory... 

T. D. (2004) Ensemble-averaged variational transition state theory with optimized multidimensional tunneling for enzyme kinetics and other condensed-phase reactions,... 

The AG value deduced from the PMF is corrected by replacing classical vibrational partition functions by their quantum homolog. Recrossing, tunnelling and non-classical reflection effects can be included in the transmission coefficient by various procedures. This ensemble-average variational transition state theory with multidimensional tunnelling (EA-VTST/MT) method was applied to proton and hydride transfers in various enzymes such as yeast enolase, liver alcohol dehydrogenase and triosephosphate isomerase. For a review, see ref. 3 and the chapter by J. Gao in this book. 

EA-VTST Ensemble-averaged variational transition state theory... 

Tmhlar DG, Gao JL, Garcia-Viloca M, Alhambra C, Corchado J, Sanchez ML, Poulsen TD (2004) Ensemble-averaged variational transition state theory with optimized multidimensional tunneling for enzyme kinetics and other condensed-phase reactions, hit J Quantum Chem 100(6) 1136-1152... 

ENSEMBLE-AVERAGED VARIATIONAL TRANSITION STATE THEORY... 

Ensemble-Averaged Variational Transition State Theory 207... 

Poulsen, Int. J. Quantum Chem., 100, 1136 (2004). Ensemble-Averaged Variational Transition State Theory with Optimized Multidimensional Tunneling for Enzyme Kinetics and Other Condensed-Phase Reactions. 

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