LAUSR

Abstract The kinetics of the reaction between propylene carbonate (PC) and OH radical is intensively studied using the master equation/Rice–Ramsperger–Kassel–Marcus (ME/RRKM) rate model, which includes hindered internal rotation and tunneling corrections, on the potential energy surface mapped out at the CCSD(T)/CBS//M06-2X/aug-cc-pVTZ level. Consistent with scattered literature data, the total rate constants are found to be pressure-independent and negatively temperature-dependent as ktot(T) = 1.27 × 10−3 × T−3.21 × exp(−446.2 K/T) cm3/molecule/s in the range of 200–500 K and 10–760 Torr, in which the reaction favors at the Cα site to form the dominant product PC-α. The following unimolecular reactions of three PC radicals are also investigated.