DFT characterization of the first step of methyl acrylate polymerization: Performance of modern functionals in the complete basis limit


YAVUZ İ. , ÇİFTÇİOĞLU G. A.

COMPUTATIONAL AND THEORETICAL CHEMISTRY, cilt.978, ss.88-97, 2011 (SCI İndekslerine Giren Dergi) identifier identifier

  • Cilt numarası: 978
  • Basım Tarihi: 2011
  • Doi Numarası: 10.1016/j.comptc.2011.09.043
  • Dergi Adı: COMPUTATIONAL AND THEORETICAL CHEMISTRY
  • Sayfa Sayıları: ss.88-97

Özet

We obtain values of the reaction barrier for the reaction of methyl acrylate CH2=CHCOOCH3 (MA) with the radical CH3CHCOOCH3 (HMA(center dot)) by density functional theory (DFT) using a variety of functionals and basis sets. Structures for the reactants and the transition state are optimized in B3LYP/cc-pVTZ. We extrapolate energies for these structures to the complete basis set (CBS) limit for each of the functionals B3LYP, PBE, TPSS, BMK, HSE2PBE, mPW1PW91. B97-1, wB97-XD, and M06-2X. The extrapolation follows the energies obtained by the basis sets cc-pVnZ with n = 2, 3, and 4. The estimate of the barrier height is sensitive to the basis and the choice of functional.