Exploring the kinetics and mechanism of C2F5C(O)CF(CF3)2 reaction with hydrogen radical

• (1) The C 6 F 12 O + H reaction was computationally explored under conditions relevant for combustion. • (2) The energetics of the relevant stationary points were computed with ab initio quantum chemistry method. • (3) RRKM/master-equation simulations were used to determine the temperature or pressure dependence elementary rate coefficients. • (4) H additions to C=O bond and their subsequent β-C-C scissions greatly contribute to the overall kinetics. This work combined high-level quantum chemistry calculations with RRKM/master-equation simulations to gain insight into reactions between C 6 F 12 O and hydrogen radical under combustion conditions. The energetics for all stationary points on potential energy surface were determined at CCSD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p) level of theory. RRKM/master-equation calculations were utilized to simulate the title reaction over a wide range of temperatures and pressures, i.e. 300-3000 K and 0.01-100 atm. Kinetic and mechanistic analyses demonstrate that hydrogen addition to initial adduct C 2 F 5 CFCOH(CF 3 ) 2 and two dissociations from adduct (CF 3 ) 2 CFCHOC 2 F 5 to CF 3 CF 2 COH + CF 3 CFCF 3 and (CF 3 ) 2 CFCOH) + CF 3 CF 2 conjointly dominate the overall kinetics over the investigated temperatures and pressures.