The separation of the reaction coordinate in transition state theory: Regularity and dimensionality reduction resulting from local symmetry

2019 ◽  
Vol 150 (16) ◽  
pp. 164310
Author(s):  
J. C. Lorquet
Keyword(s):  
Transition State ◽  
Dimensionality Reduction ◽  
Transition State Theory ◽  
Local Symmetry ◽  
State Theory ◽  
Reaction Coordinate

Bimolecular Reactions, Transition-State Theory

2018 ◽  
Author(s):  
Niels Engholm Henriksen ◽  
Flemming Yssing Hansen
Keyword(s):  
Transition State ◽  
Saddle Point ◽  
Transition State Theory ◽  
Classical Mechanics ◽  
Small Degree ◽  
State Theory ◽  
Reaction Coordinate ◽  
Partition Functions ◽  
Bimolecular Reactions ◽  
Activated Complex

This chapter discusses an approximate approach—transition-state theory—to the calculation of rate constants for bimolecular reactions. A reaction coordinate is identified from a normal-mode coordinate analysis of the activated complex, that is, the supermolecule on the saddle-point of the potential energy surface. Motion along this coordinate is treated by classical mechanics and recrossings of the saddle point from the product to the reactant side are neglected, leading to the result of conventional transition-state theory expressed in terms of relevant partition functions. Various alternative derivations are presented. Corrections that incorporate quantum mechanical tunnelling along the reaction coordinate are described. Tunnelling through an Eckart barrier is discussed and the approximate Wigner tunnelling correction factor is derived in the limit of a small degree of tunnelling. It concludes with applications of transition-state theory to, for example, the F + H2 reaction, and comparisons with results based on quasi-classical mechanics as well as exact quantum mechanics.

scholarly journals Association of Cl with C2H2by unified variable-reaction-coordinate and reaction-path variational transition-state theory

2020 ◽  
Vol 117 (11) ◽  
pp. 5610-5616
Author(s):  
Linyao Zhang ◽  
Donald G. Truhlar ◽  
Shaozeng Sun
Keyword(s):  
High Pressure ◽  
Transition State ◽  
Transition State Theory ◽  
Reaction Path ◽  
State Theory ◽  
Reaction Coordinate ◽  
Acetylene Molecule ◽  
Variational Transition State Theory ◽  
Pressure Limit ◽  
Variational Transition State

Barrierless unimolecular association reactions are prominent in atmospheric and combustion mechanisms but are challenging for both experiment and kinetics theory. A key datum for understanding the pressure dependence of association and dissociation reactions is the high-pressure limit, but this is often available experimentally only by extrapolation. Here we calculate the high-pressure limit for the addition of a chlorine atom to acetylene molecule (Cl + C2H2→C2H2Cl). This reaction has outer and inner transition states in series; the outer transition state is barrierless, and it is necessary to use different theoretical frameworks to treat the two kinds of transition state. Here we study the reaction in the high-pressure limit using multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) at the outer transition state and reaction-path variational transition state theory (RP-VTST) at the inner turning point; then we combine the results with the canonical unified statistical (CUS) theory. The calculations are based on a density functional validated against the W3X-L method, which is based on coupled cluster theory with single, double, and triple excitations and a quasiperturbative treatment of connected quadruple excitations [CCSDT(Q)], and the computed rate constants are in good agreement with some of the experimental results. The chlorovinyl (C2H2Cl) adduct has two isomers that are equilibrium structures of a double-well C≡C–H bending potential. Two procedures are used to calculate the vibrational partition function of chlorovinyl; one treats the two isomers separately and the other solves the anharmonic energy levels of the double well. We use these results to calculate the standard-state free energy and equilibrium constant of the reaction.

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