scholarly journals Transition state theory approach to polymer escape from a one dimensional potential well

2015 ◽  
Vol 142 (22) ◽  
pp. 224906 ◽  
Author(s):  
Harri Mökkönen ◽  
Timo Ikonen ◽  
Tapio Ala-Nissila ◽  
Hannes Jónsson
Keyword(s):  
Transition State ◽  
Transition State Theory ◽  
State Theory ◽  
Theory Approach ◽  
Potential Well ◽  
One Dimensional

Quantum mechanical tunnelling in the processes D + H2 → DH + H and CH4 + H → CH3 + H2. Eckart's tunnelling corrections for rate constants given by ab initio calculations

1979 ◽  
Vol 44 (12) ◽  
pp. 3452-3457 ◽  
Author(s):  
Petr Čársky
Keyword(s):  
Transition State ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Rate Constants ◽  
Transition State Theory ◽  
State Theory ◽  
Quantum Mechanical ◽  
Rate Data ◽  
Dimensional Approach ◽  
One Dimensional

Results of the best reported ab initio calculations are used to evaluate the rate constants of the title processes by means of the transition state theory. The computed rate constants are corrected for the quantum mechanical tunnelling by the Eckart's one-dimensional approach and comparison is made with experimental rate data

Tunneling in the Presence of a Bath: A Generalized Transition State Theory Approach

1994 ◽  
Vol 98 (34) ◽  
pp. 8396-8405 ◽  
Author(s):  
Donald G. Truhlar ◽  
Yi-Ping Liu ◽  
Gregory K. Schenter ◽  
Bruce C. Garrett
Keyword(s):  
Transition State ◽  
Transition State Theory ◽  
State Theory ◽  
Theory Approach

scholarly journals Application of one-dimensional semiclassical transition state theory to the CH 3 OH + H ⇌ CH 2 OH/CH 3 O + H 2 reactions

2018 ◽  
Vol 376 (2115) ◽  
pp. 20170147 ◽  
Author(s):  
Xiao Shan ◽  
David C. Clary
Keyword(s):  
Transition State ◽  
Rate Constants ◽  
Transition State Theory ◽  
Single Point ◽  
Computational Cost ◽  
State Theory ◽  
Reverse Direction ◽  
Point Energy ◽  
One Dimensional ◽  
Theory Calculation

The rate constants of the two branches of H-abstractions from CH 3 OH by the H-atom and the corresponding reactions in the reverse direction are calculated using the one-dimensional semiclassical transition state theory (1D SCTST). In this method, only the reaction mode vibration of the transition state (TS) is treated anharmonically, while the remaining internal degrees of freedom are treated as they would have been in a standard TS theory calculation. A total of eight ab initio single-point energy calculations are performed in addition to the computational cost of a standard TS theory calculation. This allows a second-order Richardson extrapolation method to be employed to improve the numerical estimation of the third- and fourth-order derivatives, which in turn are used in the calculation of the anharmonic constant. Hindered-rotor (HR) vibrations are identified in the equilibrium states of CH 3 OH and CH 2 OH, and the TSs of the reactions. The partition function of the HRs are calculated using both a simple harmonic oscillator model and a more sophisticated one-dimensional torsional eigenvalue summation (1D TES) method. The 1D TES method can be easily adapted in 1D SCTST computation. The resulting 1D SCTST with 1D TES rate constants show good agreement to previous theoretical and experimental works. The effects of the HR on rate constants for different reactions are also investigated. This article is part of the theme issue ‘Modern theoretical chemistry’.

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