How Well Can Theory Predict Addition-Fragmentation Equilibrium Constants in RAFT Polymerization?

High level ab initio molecular orbital calculations are used to study the addition-fragmentation equilibrium constants of S-S'-bis(methyl-2-propionate)-trithiocarbonate mediated polymerization of methyl acrylate in toluene at -30 degrees C. The results, which show strong solvent and chain length effects, are in good order of magnitude agreement with recent experimental results for a closely related system.