Benchmark Study of Density Functionals for the Insertions of Olefin and
Polar Monomers Catalyzed by α-Diimine Palladium Complexes
Abstract
The performance of a series of density functionals has been tested for
the insertions of ethylene, methyl acrylate (MA), and vinyl bromide (VB)
catalyzed by α-diimine palladium complexes. Sixty-seven density
functionals are screened, and the results are compared with available
experimental data. Eleven hybrid functionals (M06, BHandH, mPW1PW91,
HSEh1PBE, mPW3PBE, LC-ωPBE, mPW1PBE, PBE0, M06-HF, M06-2X, M05-2X)
showed better performance in the insertions of both ethylene and MA, and
could be therefore suitable for ethylene-MA copolymerization. Meanwhile,
three GGA (PW91PW91, HCTH, HCTH407), two meta-GGA (TPSSTPSS,
tHCTH), and ten hybrid functionals (M06, BHandH, TPSSh, B971, B98,
B1B95, PBE0, M06-2X, tHCTHhyb, M05-2X) perform well in the ethylene-VB
copolymerization. Besides, nine D3 or D3BJ augmented functionals are
found to be suitable for both copolymerization systems. The D2
dispersion correction overestimated insertion energy barriers of these
monomers and is unsuitable for such copolymerization. In addition, the
double-zeta basis set is found to be sufficient for solvation
single-point calculation of these systems.