“Experimental and Computational Investigations on the Tropospheric Photo-oxidation Reactions of 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol Initiated by OH radicals and Cl atoms”
A. Kumar, S. Gonu, S. Vijayakumar, C. B. Ramya & B. Rajakumar. J. Phys. Chem. A. 2021, 125(2), 523-535.

The gas phase kinetics for the reactions of OH radicals and Cl atoms with 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol (HF2M2P) were measured between the temperatures 268 and 363 K using relative rate experimental technique. Methane and acetonitrile were used as reference compounds to measure the rate coefficients of the title reactions. For the reactions of HF2M2P with OH radicals and Cl atoms, the rate coefficients were measured to be (7.07 ± 1.21) × 10-15 and (2.85 ± 0.54) × 10-14 cm3 molecule-1 s-1 respectively at 298 K. The obtained Arrhenius expressions for the reactions of HF2M2P with OH radicals and Cl atoms are k_(HF2M2P+OH)^(Exp-(268-363K))= (7.84 ± 0.75) × 10-14 exp [-(717 ± 59)/T] and k_(HF2M2P+Cl)^(Exp-(268-363K))= (3.21 ± 0.45) × 10-12 exp [-(1395 ± 83)/T] cm3 molecule-1 s-1. In addition to experimental measurements, computational kinetic calculations were also performed for the title reactions at M06-2X/MG3S//M06-2X/6-31+G(d,p) level of theory using advanced methods such as Canonical Variational Transition state theory (CVT) coupled with Small Curvature Tunnelling corrections (SCT) in the temperatures between 200 and 400 K. Theoretical calculations reveal that the H-abstraction from the CH3 group is more favourable reaction channel than that from the OH group. Thermochemistry, branching ratios, cumulative atmospheric lifetime (CAL), global warming potential (GWP), acidification potential (AP) and photochemical ozone creation potential (POCP) of the HF2M2P were calculated in the present investigation.