Transition State Theory with Multidimensional Tunneling

Variational Transition State Theory with Multidimensional Tunneling 

Raymond Daudel, Georges Leroy, Daniel Peeters, and Michael Sana, 1983 

This review describes the appHcation of variational transition state theory (VTST) to the calculation of chemical reaction rates. In 1985, two of us, together with Alan D. Isaacson, wrote a book chapter on this subject entitled Generalized Transition State Theory for the multi-volume series entitled Theory of Chemical Reaction Dynamics Since that time, VTST has undergone 

Reviews in Computational Chemistry, Volume 23 edited by Kenny B. Lipkowitz and Thomas R. Cundari Copyright 2007 Wiley-VCH, John Wiley Sons, Inc. 

A word on nomenclature is in order here. When we say transition state theory, we refer to the various versions of the theory, with or without including tunneling. When we want to be more specific, we may say conventional 

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Fernandez-Ramos A, Ellingson BA, Garrett BC, Trahlar DG (2007) Variational transition state theory with multidimensional tunneling. In Lipkowitz KB, Cundari TR, Boyd DB (eds) Reviews in Computational Chemistry, Vol 23. Wiley-VCH, New York, p 125... 

Antonio Fernandez-Ramos, Benjamin A. Ellingson, Bruce C. Garrett, and Donald G. Truhlar, Variational Transition State Theory with Multidimensional Tunneling. 

The higher dimensionality of polyatomic reactions makes them more of a challenge to treat theoretically. Variational transition state theory with multidimensional tunneling has been developed to allow calculations for a wide variety of polyatomic systems. In this section we consider issues that arise when treating polyatomic systems. The Cl -1- CH4 reaction provides a good system for this pur-... 

Ensemble-A erage Variational Transition State Theory with Multidimensional Tunnelling... 

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. 

Pu JZ, Corchado JC, Truhlar DG (2001) Test of variational transition state theory with multidimensional tunneling contributions against tm accurate fuU-dimensional rate constant calculation fora six-atom system. J Chem Phys 115 6266-6267... 

Accurate quantum mechanical calculations on the D -f H2 reaction allow one to test the quantitative predictive ability of variational transition state theory with multidimensional tunneling contributions. Such VTST calculations agree with accurate quantum dynamics with an average eiTor of only... 

Variational Transition State Theory With Multidimensional Tunneling Contributions Against an Accurate Full-Dimensional Rate Constant Calculation for a Six-Atom System. 

Allison TC, Trahlar DG (1998) Testing the accuracy of practical semiclassical methods variational transition state theory with optimized multidimensional tunnelling. In Thompson DL (ed) Modern Methods for Multidimensional Dynamics Computations in Chemistry. World Scientific, Singapore, p 618... 

Table 6.2 Tests of Variational Transition State Theory by Comparing with Exact Quantum Calculations (Extracted from Allison, T. C. and Truhlar, D. G. Testing the accuracy of practical semiclassical methods variational transition state theory with optimized multidimensional tunneling, in Thompson, D. L., Ed. Modem methods for multidimensional dynamics computations in chemistry, World Scientific, Singapore 1998. pp 618-712. This reference quotes results on many more reactions and BO surfaces over broad temperature ranges.)The numbers in the table are ratios of the results of the approximate calculation to the quantum calculation, all at 300 K...

T. V. Albu, J. C. Corchado, D. G. Truhlar, J. Phys. Chem. A 105, 8465 (2001). Molecular Mechanics for Chemical Reactions A Standard Strategy for Using Multiconfiguration Molecular Mechanics for Variational Transition State Theory with Optimized Multidimensional Tunneling. 

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

Mechanics for Chemical Reactions A Standard Strategy for Using Multiconfiguration Molecular Mechanics for Variational Transition State Theory with Optimized Multidimensional Tunneling. 

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... 

Albu TV, Corchado JC, Truhlar DG (2001) Molecular mechanics for chemical reactions a standard strategy for using multiconfiguration molecular mechanics for variational transition state theory with optimized multidimensional tunneling. J Phys Chem A 105 8465-8487... 

Computations in Chemistry, D. L. Thompson, Ed., World Scientific, Singapore, 1998, pp. 618-712. Testing the Accuracy of Practical Semiclassical Methods Variational Transition State Theory With Optimized Multidimensional Tunneling. 

The rate of hydrogen transfer can be calculated using the direct dynamics approach of Truhlar and co-workers which combines canonical variational transition state theory (CVT) [82, 83] with semi-classical multidimensional tunnelling corrections [84], The rate constant is calculated using [83] ... 

In ESP theory [30-32] we treat the system by the same methods that we would use in the gas phase except that in the nontunneling part of the calculation we replace V(R) by TT(R), and in the tunneling part we approximate V(R) by TT(R) or a function of TT(R). Next we review what that entails. In particular we will review the application of variational transition state theory [21-25] with optimized multidimensional tunneling [33,34] to liquid-phase reactions for the case [31,32] in which TT(R) is calculated from V(R) by... 

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