Issue 8, 2006

Quantum reactive scattering of H + hydrocarbon reactions

Abstract

A practical quantum-dynamical method is described for predicting accurate rate constants for general chemical reactions. The ab initio potential energy surfaces for these reactions can be built from a minimal number of grid points (average of 50 points) and expressed in terms of analytical functionals. All the degrees of freedom except the breaking and forming bonds are optimised using the MP2 method with a cc-pVTZ basis set. Single point energies are calculated on the optimised geometries at the CCSD(T) level of theory with the same basis set. The dynamics of these reactions occur on effective reduced dimensionality hyper-surfaces accounting for the zero-point energy of the optimised degrees of freedom. Bonds being broken and formed are treated with explicit hyperspherical time independent quantum dynamics. Application of the method to the H + CH4 → H2 + CH3, H + C2H6 → H2 + C2H5, H + C3H8 → H2 + n-C3H7/H2 + i-C3H7 and H + CH3OH → H2 + CH3O/H2 + CH2OH reactions illustrate the potential of the approach in predicting rate constants, kinetic isotope effects and branching ratios. All studied reactions exhibit large quantum tunneling in the rate constants at lower temperatures. These quantum calculations compare well with the experimental results.

Graphical abstract: Quantum reactive scattering of H + hydrocarbon reactions

Article information

Article type
Invited Article
Submitted
13 Oct 2005
Accepted
05 Dec 2005
First published
20 Jan 2006

Phys. Chem. Chem. Phys., 2006,8, 917-925

Quantum reactive scattering of H + hydrocarbon reactions

B. Kerkeni and D. C. Clary, Phys. Chem. Chem. Phys., 2006, 8, 917 DOI: 10.1039/B514563P

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