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, vol.978, pp.88-97, 2011 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 978
  • Publication Date: 2011
  • Doi Number: 10.1016/j.comptc.2011.09.043
  • Title of Journal : COMPUTATIONAL AND THEORETICAL CHEMISTRY
  • Page Numbers: pp.88-97

Abstract

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.