Abstract
Experimental work on the OH-initiated oxidation reactionsof fluorotelomer aldehydes (FTALs) strongly suggests thatthe respective rate coefficients do not depend on the sizeof the CxF2x+1 fluoroalkyl chain. FTALs hence representa challenging test to our multiconformer transition statetheory (MC-TST) protocol based on constrained transition state randomization (CTSR), since the calculated ratecoefficients should not show significant variations with increasing values of x. In this work we apply the MC-TST/CTSR protocol to the x = 2, 3 cases and calculate both rate coefficients at 298.15 K with a value ofk = (2.4±1.4)×10-12 cm3 molecule-1 s-1 , practicallycoincident with the recommended experimental value ofkexp = (2.8±1.4)×10-12 cm3 molecule-1 s-1. We alsoshow that the use of tunneling corrections based on improved semiclassical TST is critical in obtaining Arrhenius-Kooij curves with a correct behavior at lower temperatures.
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