posted on 2024-02-05, 07:43authored byHao Du, Masahiro Sato, Atsushi Komuro, Ryo Ono
To determine the H-abstraction reaction probabilities
of H/O/OH
radicals with a polypropylene (PP) surface, a first-principles calculation
was performed based on the DLPNO–CCSD(T)/CBS//M06-2X-D3/def-TZVP
theory level. The PP chain model used in this study was 2,4,6-trimethylheptane.
The rate constants of the H/O/OH radicals with the isolated PP chain
model were calculated based on the conventional transition-state theory.
By comparing the experimental values and considering the error factors
and their compensation, it was concluded that the orders of magnitude
of the predicted rate constants were accurate. The resulting rate
constants were converted to reaction probabilities between the H/O/OH
radicals and the PP surface. The method used in this study is applicable
for obtaining theoretical values of surface reaction probabilities
based on first-principles calculations. The calculation at the DLPNO–CCSD(T)/CBS
theory level has high accuracy but consumes a large amount of computational
resources. The study also demonstrated that the double-hybrid functionals,
wB97x-2-D3(BJ) and rev-DSD-PBEP86-D3(BJ), with a 3-ζ or 4-ζ
basis set, could reproduce the electronic energy values obtained from
DLPNO–CCSD(T)/CBS while using only approximately 1/100 of the
computational resources required by the latter under our computer
configuration.