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Temperature dependence of the thermal rate constants and kinetic isotopeeffects (KIE) of the CN + C2H6 gas-phase hydrogen abstraction reaction wastheoretically determined within the 25-1000 K temperature range, i.e., fromultra-low to high-temperature regimes. Based on a recently developedfull-dimensional analytical potential energy surface fitted to highly accurateexplicitly correlated ab initio calculations, three different kinetic theorieswere used: canonical variational transition state theory (CVT), quasiclassicaltrajectory theory (QCT), and ring polymer molecular dynamics (RPMD) method forthe computation of rate constants. We found that the thermal rate constantsobtained with the three theories show a V-shaped temperature dependence, with apronounced minimum near 200 K, qualitatively reproducing the experimentalmeasurements. Among the three methods used in this work, the QCT and RPMDmethods have the best agreement with the experiment at low and hightemperatures, respectively. The significant increase in the rate constant atultra-low temperatures in this very exothermic and practically barrierlessreaction can be attributed to the large value of the impact parameter, rulingout the role of the tunneling effect and the intermediate complexes in theentrance channel. The theoretical H/D KIE depicted a normal behaviour, i.e.,values greater than unity, emulating the experimental measurements and previoustheoretical results. Finally, the discrepancies between theory and experimentswere analysed as a function of several factors, such as limitations of thekinetics theories and the potential energy surface, as well as theuncertainties in the experimental measurements.

Kinetic study of the CN + C2H6 hydrogen abstraction reaction based on an analytical potential energy surface