A reactive
Molecular Dynamics (MD) study of toluene oxidation at
high temperatures under externally applied electrostatic fields has
been performed. The impact of the modeling of local charge distribution
has been investigated by comparing the widely used Charge Equilibration
(QEq) method with the Charge Transfer with Polarization Current Equalization
(QTPIE) method, which shields charge transfers up to atomic orbitals
and introduces molecular polarization. Using the latter method, it
is possible to improve the computation of the atomic charges, which
are a critical aspect for the numerical study of electric fields,
and to capture important effects of the electric field on rotational
and vibrational energies of the toluene molecule. Results show that
a more comprehensive treatment of inter- and intramolecular charge
distribution achieved through the QTPIE method leads to substantially
different applied forces and oxidation rates of toluene compared to
the QEq method. Using the QTPIE method, no significant effects of
the electrostatic field on the toluene oxidation rate were observed
for the range of temperatures and pressures studied here, which is
in disagreement with the results obtained with the QEq method where
a clear impact of the electrostatic field on the average oxidation
rate was found. Therefore, when studying electric field effects with
MD simulations, the choice of the method used for the charge equilibration
is a key modeling assumption whose impact should be carefully evaluated.