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Article Dans Une Revue Chemical Physics Année : 2016

Quantum chemistry and dynamics of the abstraction reaction of H atoms from formaldehyde

Résumé

This work reports a reduced dimensionality rate constant calculation of the H-abstraction reaction from formaldehyde. Quantum scattering calculations are performed treating explicitly the bonds being broken and formed. Geometry optimisations and frequency calculations are done at the MP2/cc-pVTZ level while energies are calculated with the CCSD(T) method. An analytical potential energy surface was developed from a relatively small number of grid points. When compared to semi-classical approaches, the quantum scattering calculations show that quantum tunnelling yields large contributions at low temperatures. At 200 K, we note a difference of about 5 orders of magnitude between Transition State Theory (TST) and quantum rate constants. Our predicted results show that the quantum and the CVT/SCT rate constants are in reasonable agreement with the available experiment at high temperatures, but that the last one gives better agreement to experimental results at low temperatures.

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Chimie
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Dates et versions

hal-01316471 , version 1 (17-05-2016)

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A. Siai, I. Oueslati, Boutheina Kerkeni. Quantum chemistry and dynamics of the abstraction reaction of H atoms from formaldehyde. Chemical Physics, 2016, 474, pp.44-51. ⟨10.1016/j.chemphys.2016.05.007⟩. ⟨hal-01316471⟩
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