Center for Molecular Modeling - L. Radom

Ab initio thermochemistry and Kinetics of Hydrogen Abstraction by Methyl Radical from Polycyclic Aromatic Hydrocarbons

wim — Mon, 03 Oct 2011 07:09:00 +0000

K. Hemelsoet, V. Van Speybroeck, D. Moran, G.B. Marin, L. Radom, M. Waroquier

Journal of Physical Chemistry A

110 (50), 13624-13631

2006

Abstract

Thermodynamic and kinetic properties relating to hydrogen abstraction by methyl radical from various sites in polycyclic aromatic hydrocarbons (PAHs) have been investigated. The reaction enthalpies (298 K), barriers (0 K), and activation energies and pre-exponential factors (700−1100 K), have been calculated by means of density functional theory, specifically with B3-LYP/6-311G(d,p) geometries, followed by BMK/6-311+G(3df,2p) single-point energy calculations. For uncongested sites in the PAHs, a reasonable correlation is obtained between reactivities (as characterized by the reaction barriers) and reaction enthalpies. This is reflected in a Bell−Evans−Polanyi (BEP) relationship. However, for congested sites, abstraction is accompanied both by lower reaction enthalpies (due to relief of steric strain) and also by reduced reactivities (due to significantly increased steric hindrance effects in the transition structures), so that the BEP relationship does not hold. In addition, the reaction enthalpies and kinetic parameters for the series of linear acenes indicate that abstraction is more difficult from the central rings.

DOI

http://dx.doi.org/10.1021/jp065141n

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06 j. chem. phys. A 110(50)13624 hemelsoet.pdf

An assessment of theoretical procedures for predicting the thermochemistry and kinetics of hydrogen abstraction by methyl radical from benzene

wim — Fri, 30 Sep 2011 14:45:12 +0000

K. Hemelsoet, D. Moran, V. Van Speybroeck, M. Waroquier, L. Radom

Journal of Physical Chemistry A

110 (28), 8942-8951

2006

Abstract

The reaction enthalpy (298 K), barrier (0 K), and activation energy and preexponential factor (600−800 K) have been examined computationally for the abstraction of hydrogen from benzene by the methyl radical, to assess their sensitivity to the applied level of theory. The computational methods considered include high-level composite procedures, including W1, G3-RAD, G3(MP2)-RAD, and CBS-QB3, as well as conventional ab initio and density functional theory (DFT) methods, with the latter two classes employing the 6-31G(d), 6-31+G(d,p) and/or 6-311+G(3df,2p) basis sets, and including ZPVE/thermal corrections obtained from 6-31G(d) or 6-31+G(d,p) calculations. Virtually all the theoretical procedures except UMP2 are found to give geometries that are suitable for subsequent calculation of the reaction enthalpy and barrier. For the reaction enthalpy, W1, G3-RAD, and URCCSD(T) give best agreement with experiment, while the large-basis-set DFT procedures slightly underestimate the endothermicity. The reaction barrier is slightly more sensitive to the choice of basis set and/or correlation level, with URCCSD(T) and the low-cost BMK method providing values in close agreement with the benchmark G3-RAD value. Inspection of the theoretically calculated rate parameters reveals a minor dependence on the level of theory for the preexponential factor. There is more sensitivity for the activation energy, with a reasonable agreement with experiment being obtained for the G3 methods and the hybrid functionals BMK, BB1K, and MPW1K, especially in combination with the 6-311+G(3df,2p) basis set. Overall, the high-level G3-RAD composite procedure, URCCSD(T), and the cost-effective DFT methods BMK, BB1K, and MPW1K give the best results among the methods assessed for calculating the thermochemistry and kinetics of hydrogen abstraction by the methyl radical from benzene.

DOI

http://dx.doi.org/10.1021/jp061823z

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06 j. chem. phys. A 110(28)8942 hemelsoet.pdf

An Evaluation of the Influence of the Level of Theory on DFT-based Reactivity Descriptors

wim — Tue, 18 Oct 2011 08:32:37 +0000

K. Hemelsoet, V. Van Speybroeck, D. Moran, L. Radom, M. Waroquier

Poster

Conference / event / venue

Reactivity Symposium, Theoretical aspects of reactivity

Brussels, Belgium

Tuesday, 5 April, 2005 to Thursday, 7 April, 2005

An Evaluation of the Level of Theory on DFT-based Reactivity Descriptors

wim — Tue, 18 Oct 2011 08:27:15 +0000

K. Hemelsoet, V. Van Speybroeck, D. Moran, L. Radom, M. Waroquier

Poster

Conference / event / venue

DFT2005

Geneva, Switzerland

Sunday, 11 September, 2005 to Thursday, 15 September, 2005

Reactivity of Radical Reactions involving Polycyclic Aromatic Hydrocarbons

wim — Mon, 17 Oct 2011 11:37:06 +0000

K. Hemelsoet, V. Van Speybroeck, D. Moran, L. Radom, M. Waroquier

Talk

Conference / event / venue

Reactivity Symposium, Theoretical aspects of reactivity

Brussels (Belgium)

Wednesday, 5 April, 2006 to Friday, 7 April, 2006