  For the first time, the combination of experimental preparation and results
of fully atomistic simulations of an oligoelectrolyte multilayer (OEM) made of
poly(diallyl dimethyl ammonium chloride)/poly(styrene sulfonate sodium salt)
(PDADMAC/PSS) is presented. The layer-by-layer growth was carried out by
dipping silica substrates in oligoelectrolyte solutions and was modeled by
means of atomistic molecular dynamics simulations with a protocol that mimics
the experimental procedure up to the assembly of four layers. Measurements of
OEM thickness, surface roughness and amount of adsorbed oligoelectrolyte chains
obtained from both approaches are compared. A good agreement between simulated
and experimental results was found, with some deviations due to intrinsic
limitations of both methods. However, the combination of information extracted
from simulations to support the analysis of experimental data can overcome such
restrictions and improve the interpretation of experimental results. On the
other hand, processes dominated by slower kinetics, like the destabilization of
adsorbed layers upon equilibration with the surrounding environment, are out of
reach for the simulation modeling approach, but they can be investigated by
monitoring in situ the oligoelectrolyte adsorption during the assembly process.
This demonstrates how the synergistic use of simulation and experiments
improves the knowledge of OEM properties down to the molecular scale.
