scholarly journals Nonadiabatic quantum transition-state theory in the golden-rule limit. II. Overcoming the pitfalls of the saddle-point and semiclassical approximations

2019 ◽  
Vol 151 (21) ◽  
pp. 214101 ◽  
Author(s):  
Wei Fang ◽  
Manish J. Thapa ◽  
Jeremy O. Richardson
Keyword(s):  
Transition State ◽  
Saddle Point ◽  
Transition State Theory ◽  
Golden Rule ◽  
State Theory ◽  
Quantum Transition ◽  
Semiclassical Approximations

scholarly journals Revisiting nuclear tunnelling in the aqueous ferrous–ferric electron transfer

2020 ◽  
Vol 22 (19) ◽  
pp. 10687-10698 ◽  
Author(s):  
Wei Fang ◽  
Rhiannon A. Zarotiadis ◽  
Jeremy O. Richardson
Keyword(s):  
Electron Transfer ◽  
Transition State ◽  
Transition State Theory ◽  
Golden Rule ◽  
State Theory ◽  
Quantum Transition ◽  
Quantum Regime ◽  
Order Of Magnitude ◽  
Boson Model

We find that golden-rule quantum transition-state theory predicts nearly an order of magnitude less tunnelling than some of the previous estimates. This may indicate that the spin-boson model of electron transfer is not valid in the quantum regime.

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.

Comment on Quantum Transition State Theory

1996 ◽  
Vol 100 (29) ◽  
pp. 11893-11902 ◽  
Author(s):  
Stuart A. Rice ◽  
Soonmin Jang ◽  
Meishan Zhao
Keyword(s):  
Transition State ◽  
Transition State Theory ◽  
State Theory ◽  
Quantum Transition

Properties of Quantum Transition State Theory and Its Corrections

1996 ◽  
Vol 100 (4) ◽  
pp. 1137-1143 ◽  
Author(s):  
Nancy Fisher Hansen ◽  
Hans C. Andersen
Keyword(s):  
Transition State ◽  
Transition State Theory ◽  
State Theory ◽  
Quantum Transition
Sign in / Sign up

Export Citation Format

Share Document