Reaction cross sections and thermal rate constant for Cl− + CH3Br → ClCH3 + Br− from J-dependent quantum scattering calculations
文献情報
Carsten Hennig, Stefan Schmatz
Employing dimensionality-reduced time-independent quantum scattering theory and summation over all possible total angular momentum states, initial-state selected reaction cross sections for the exothermic gas-phase bimolecular nucleophilic substitution (SN2) reaction Cl− + CH3Br → ClCH3 + Br− have been calculated. The carbon–halogen bonds and the rotation of the methyl halides are taken into account. In agreement with previous calculations for J = 0, initial rotational motion of CH3Br decreases the reaction probability and consequently the cross sections. The experimentally obtained thermal rate constant for 300 K is reproduced within the experimental error. For lower temperatures, it is calculated to be below the experimental values but shows the same strong increase for T → 0.
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