Quantum chemical and conventional TST calculations of rate constants for the OH + alkane reaction

• Published in: Chemical physics Vol. 310; no. 1; pp. 213 - 223
• Main Authors: Bravo-Pérez, Graciela, Alvarez-Idaboy, J. Raúl, Jiménez, Annia Galano, Cruz-Torres, Armando
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 04-04-2005
• ISSN: 0301-0104
• DOI: 10.1016/j.chemphys.2004.10.031

Reactions of OH with methane, ethane, propane,
i-butane, and
n-butane have been modeled using ab initio (MP2) and hybrid DFT (BHandHLYP) methods, and the 6-311G(d,p) basis set. Furthermore, single-point calculations at the CCSD(T) level were carried out at the optimized geometries. The rate constants have been calculated using the conventional transition-state theory (CTST). Arrhenius equations are proposed in the temperature range of 250–650 K. Hindered Internal Rotation partition functions calculations were explicitly carried out and included in the total partition functions. These corrections showed to be relevant in the determination of the pre-exponential parameters, although not so important as in the NO
3
+
alkane reactions [G. Bravo-Pérez, J.R. Alvarez-Idaboy, A. Cruz-Torres, M.E. Ruíz, J. Phys. Chem. A 106 (2002) 4645]. The explicit participation of the tunnel effect has been taken into account. The calculated rate coefficients provide a very good agreement with the experimental data. The best agreement for the overall alkane
+
OH reactions seemed to occur when the BHandHLYP geometries and partition functions are used. For propane and
i-butane, in addition to the respective secondary and tertiary H-abstraction channels, the primary one has been considered. These pathways are confirmed to be significant in spite of the large differences in activation energies between primary and secondary or primary and tertiary channels, respectively of propane and
i-butane reactions and should not be disregarded.