A Multiconformational Transition State Theory Approach to OH Tropospheric Degradation of Fluorotelomer Aldehydes

Abstract

AbstractExperimental work on the OH‐initiated oxidation reactions of fluorotelomer aldehydes (FTALs) strongly suggests that the respective rate coefficients do not depend on the size of the CxF2x+1 fluoroalkyl chain. FTALs hence represent a challenging test to our multiconformer transition state theory (MC‐TST) protocol based on constrained transition state randomization (CTSR), since the calculated rate coefficients should not show significant variations with increasing values of . In this work we apply the MC‐TST/CTSR protocol to the cases and calculate both rate coefficients at 298.15 K with a value of  cm3 molecule−1 s−1, practically coincident with the recommended experimental value of kexp=  cm3 molecule−1 s−1. We also show 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.