Ghent University Academic Bibliography

Advanced

Modeling the influence of resonance stabilization on the kinetics of hydrogen abstractions

Maarten Sabbe UGent, Aäron Vandeputte UGent, Marie-Françoise Reyniers UGent, Michel Waroquier UGent and Guy Marin UGent (2010) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 12(6). p.1278-1298
abstract
Resonance stabilization of the transition state is one of the key factors in modeling the kinetics of hydrogen abstraction reactions between hydrocarbons. A group additive model is developed which allows the prediction of rate coefficients for bimolecular hydrogen abstraction reactions over a broad range of hydrocarbons and hydrocarbon radicals between 300 and 1300 K. Group additive values for 50 groups are determined from rate coefficients determined using the high level CBS-QB3 ab initio method, corrected for tunneling and the hindered internal rotation around the transitional bond. Resonance and hyperconjugative stabilization of the transition state is accounted for by introducing 4 corrections based on the structure of the reactive moiety of the transition state. The corrections, fitted to a set of 28 reactions, are temperature-independent and reduce the mean absolute deviation on E-a to 0.7 kJ mol(-1) and to 0.05 for log A. Tunneling contributions are accounted for by using a fourth order polynomial in the activation energy. Final validation for 19 reactions yields a mean factor of deviation between group additive prediction and ab initio calculation of 2.4 at 300 K and 1.8 at 1000 K. In comparison with 6 experimental rate coefficients (600-719 K), the mean factor of deviation is less than 3.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
CENTERED RADICAL-ADDITION, TRANSITION-STATE THEORY, THEORETICAL PROCEDURES, REACTION-RATE PREDICTION, BETA-SCISSION REACTIONS, AB-INITIO, STATISTICAL FACTORS, THERMAL-REACTION, ACTIVATION-ENERGIES, THERMOCHEMICAL PROPERTIES
journal title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Phys. Chem. Chem. Phys.
volume
12
issue
6
pages
1278 - 1298
Web of Science type
Article
Web of Science id
000274072900008
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
3.453 (2010)
JCR rank
4/31 (2010)
JCR quartile
1 (2010)
ISSN
1463-9076
DOI
10.1039/b919479g
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
869755
handle
http://hdl.handle.net/1854/LU-869755
date created
2010-02-19 11:01:47
date last changed
2010-03-02 14:47:50
@article{869755,
  abstract     = {Resonance stabilization of the transition state is one of the key factors in modeling the kinetics of hydrogen abstraction reactions between hydrocarbons. A group additive model is developed which allows the prediction of rate coefficients for bimolecular hydrogen abstraction reactions over a broad range of hydrocarbons and hydrocarbon radicals between 300 and 1300 K. Group additive values for 50 groups are determined from rate coefficients determined using the high level CBS-QB3 ab initio method, corrected for tunneling and the hindered internal rotation around the transitional bond. Resonance and hyperconjugative stabilization of the transition state is accounted for by introducing 4 corrections based on the structure of the reactive moiety of the transition state. The corrections, fitted to a set of 28 reactions, are temperature-independent and reduce the mean absolute deviation on E-a to 0.7 kJ mol(-1) and to 0.05 for log A. Tunneling contributions are accounted for by using a fourth order polynomial in the activation energy. Final validation for 19 reactions yields a mean factor of deviation between group additive prediction and ab initio calculation of 2.4 at 300 K and 1.8 at 1000 K. In comparison with 6 experimental rate coefficients (600-719 K), the mean factor of deviation is less than 3.},
  author       = {Sabbe, Maarten and Vandeputte, A{\"a}ron and Reyniers, Marie-Fran\c{c}oise and Waroquier, Michel and Marin, Guy},
  issn         = {1463-9076},
  journal      = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS},
  keyword      = {CENTERED RADICAL-ADDITION,TRANSITION-STATE THEORY,THEORETICAL PROCEDURES,REACTION-RATE PREDICTION,BETA-SCISSION REACTIONS,AB-INITIO,STATISTICAL FACTORS,THERMAL-REACTION,ACTIVATION-ENERGIES,THERMOCHEMICAL PROPERTIES},
  language     = {eng},
  number       = {6},
  pages        = {1278--1298},
  title        = {Modeling the influence of resonance stabilization on the kinetics of hydrogen abstractions},
  url          = {http://dx.doi.org/10.1039/b919479g},
  volume       = {12},
  year         = {2010},
}

Chicago
Sabbe, Maarten, Aäron Vandeputte, Marie-Françoise Reyniers, Michel Waroquier, and Guy Marin. 2010. “Modeling the Influence of Resonance Stabilization on the Kinetics of Hydrogen Abstractions.” Physical Chemistry Chemical Physics 12 (6): 1278–1298.
APA
Sabbe, M., Vandeputte, A., Reyniers, M.-F., Waroquier, M., & Marin, G. (2010). Modeling the influence of resonance stabilization on the kinetics of hydrogen abstractions. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 12(6), 1278–1298.
Vancouver
1.
Sabbe M, Vandeputte A, Reyniers M-F, Waroquier M, Marin G. Modeling the influence of resonance stabilization on the kinetics of hydrogen abstractions. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2010;12(6):1278–98.
MLA
Sabbe, Maarten, Aäron Vandeputte, Marie-Françoise Reyniers, et al. “Modeling the Influence of Resonance Stabilization on the Kinetics of Hydrogen Abstractions.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 12.6 (2010): 1278–1298. Print.