Comparison of canonical variational transition state theory rate constants for hydrogen atom association with alkyl radicals and with the (111) surface of diamond

1993 ◽  
Vol 97 (45) ◽  
pp. 11706-11711 ◽  
Author(s):  
Philippe Barbarat ◽  
Cedric Accary ◽  
William L. Hase
Keyword(s):  
Hydrogen Atom ◽  
Transition State ◽  
Rate Constants ◽  
Transition State Theory ◽  
State Theory ◽  
Variational Transition State Theory ◽  
Alkyl Radicals ◽  
Variational Transition State

Computational study on the reaction of atomic chlorine with 1,2-dibromoethane (CH2BrCH2Br)

2013 ◽  
Vol 91 (11) ◽  
pp. 1123-1129 ◽  
Author(s):  
Ang-yang Yu
Keyword(s):  
Transition State ◽  
Rate Constants ◽  
Transition State Theory ◽  
Computational Study ◽  
Minimum Energy ◽  
State Theory ◽  
Basis Set ◽  
Stationary Points ◽  
Variational Transition State Theory ◽  
Variational Transition State

In this work, the reaction mechanism and kinetics of Cl + CH2BrCH2Br → products are theoretically investigated for the first time. The optimized geometries and frequencies of all of the stationary points and selected points along the minimum-energy path for the three hydrogen abstraction channels and two bromine abstraction channels are calculated at the BH&H-LYP level with the 6-311G** basis set and the energy profiles are further calculated at the CCSD(T) level of theory. The rate constants are evaluated using the conventional transition-state theory, the canonical variational transition-state theory, and the canonical variational transition-state theory with a small-curvature tunneling correction over the temperature range 200–1000 K. The results show that reaction channel 3 is the primary channel and the calculated rate constants are in good agreement with available experimental values. The three-parameter Arrhenius expression for the total rate constants over 200–1000 K is provided.

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