Center for Molecular Modeling - A.G. Vandeputte

Theoretical Study of the Thermodynamics and Kinetics of Hydrogen Abstractions from Hydrocarbons

wim — Mon, 03 Oct 2011 08:15:34 +0000

A.G. Vandeputte, M. Sabbe, M-F. Reyniers, V. Van Speybroeck, M. Waroquier, G.B. Marin

Journal of Physical Chemistry A

111 (46), 11771–11786

2007

Abstract

Thermochemical and kinetic data were calculated at four cost-effective levels of theory for a set consisting of five hydrogen abstraction reactions between hydrocarbons for which experimental data are available. The selection of a reliable, yet cost-effective method to study this type of reactions for a broad range of applications was done on the basis of comparison with experimental data or with results obtained from computationally demanding high level of theory calculations. For this benchmark study two composite methods (CBS-QB3 and G3B3) and two density functional theory (DFT) methods, MPW1PW91/6-311G(2d,d,p) and BMK/6-311G(2d,d,p), were selected. All four methods succeeded well in describing the thermochemical properties of the five studied hydrogen abstraction reactions. High-level Weizmann-1 (W1) calculations indicated that CBS-QB3 succeeds in predicting the most accurate reaction barrier for the hydrogen abstraction of methane by methyl but tends to underestimate the reaction barriers for reactions where spin contamination is observed in the transition state. Experimental rate coefficients were most accurately predicted with CBS-QB3. Therefore, CBS-QB3 was selected to investigate the influence of both the 1D hindered internal rotor treatment about the forming bond (1D-HR) and tunneling on the rate coefficients for a set of 21 hydrogen abstraction reactions. Three zero curvature tunneling (ZCT) methods were evaluated (Wigner, Skodje & Truhlar, Eckart). As the computationally more demanding centrifugal dominant small curvature semiclassical (CD-SCS) tunneling method did not yield significantly better agreement with experiment compared to the ZCT methods, CD-SCS tunneling contributions were only assessed for the hydrogen abstractions by methyl from methane and ethane. The best agreement with experimental rate coefficients was found when Eckart tunneling and 1D-HR corrections were applied. A mean deviation of a factor 6 on the rate coefficients is found for the complete set of 21 reactions at temperatures ranging from 298 to 1000 K. Tunneling corrections play a critical role in obtaining accurate rate coefficients, especially at lower temperatures, whereas the hindered rotor treatment only improves the agreement with experiment in the high-temperature range.

DOI

http://dx.doi.org/10.1021/jp075132u

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07 j. phys. chem. A 111(46)11771 vandeputte.pdf

arbon-Centered Radical Addition and β-Scission Reactions: Modeling of Activation Energies and Pre-exponential Factors

wim — Mon, 03 Oct 2011 07:52:35 +0000

M. Sabbe, A.G. Vandeputte, M-F. Reyniers, V. Van Speybroeck, M. Waroquier, G.B. Marin

Journal of Physical Chemistry A

9 (1), 124-140

2007

Abstract

A consistent set of group additive values ΔGAV° for 46 groups is derived, allowing the calculation of rate coefficients for hydrocarbon radical additions and β-scission reactions. A database of 51 rate coefficients based on CBS-QB3 calculations with corrections for hindered internal rotation was used as training set. The results of this computational method agree well with experimentally observed rate coefficients with a mean factor of deviation of 3, as benchmarked on a set of nine reactions. The temperature dependence on the resulting ΔGAV°s in the broad range of 300–1300 K is limited to ±4.5 kJ mol−1 on activation energies and to ±0.4 on logA (A: pre-exponential factor) for 90 % of the groups. Validation of the ΔGAV°s was performed for a test set of 13 reactions. In the absence of severe steric hindrance and resonance effects in the transition state, the rate coefficients predicted by group additivity are within a factor of 3 of the CBS-QB3 ab initio rate coefficients for more than 90 % of the reactions in the test set. It can thus be expected that in most cases the GA method performs even better than standard DFT calculations for which a deviation factor of 10 is generally considered to be acceptable.

DOI

http://dx.doi.org/10.1002/cphc.200700469

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07 j. phys. chem. A 111(34)8416 sabbe.pdf

Carbon‐Centered Radical Addition and ‐Scission Reactions Modeling of Activation Energies.pdf

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

wim — Tue, 13 Sep 2011 12:51:47 +0000

M. Sabbe, A.G. Vandeputte, M-F. Reyniers, M. Waroquier, G.B. Marin

Physical Chemistry Chemical Physics (PCCP)

12, 1278-1298

2010

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 Ea 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.

DOI

http://dx.doi.org/10.1039/B919479G

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10 phys. chem. chem. phys 12(6)1278 sabbe.pdf

Ab initio rate coefficients for hydrogen abstraction reactions

samuel — Thu, 06 Feb 2020 15:07:53 +0000

M. Sabbe, A.G. Vandeputte, M-F. Reyniers, V. Van Speybroeck, M. Waroquier, G.B. Marin

ISBN/ISSN:

Talk

Conference / event / venue

3rd International conference on Foundations of Molecular Modeling and Simulation (FOMMS 2006)

Blaine, WA, USA

Sunday, 9 July, 2006 to Friday, 14 July, 2006

Ab Initio Rate Coefficients for H-abstraction reactions

wim — Tue, 18 Oct 2011 08:12:58 +0000

M. Sabbe, A.G. Vandeputte, M-F. Reyniers, G.B. Marin, V. Van Speybroeck, M. Waroquier

Poster

Conference / event / venue

FOMMS (Foundations of Molecular Modeling and Simulation)

Semiahmoo Resort, US

Sunday, 9 July, 2006 to Friday, 14 July, 2006