Effective protective
coatings are an essential component of lightweight
engineering materials in a large variety of applications as they ensure
structural integrity of the base material throughout its whole service
life. Layered double hydroxides (LDHs) loaded with corrosion inhibitors
depict a promising approach to realize an active corrosion protection
for aluminum and magnesium. In this work, we employed a combination
of density functional theory and molecular dynamics simulations to
gain a deeper understanding of the influence of intercalated water
content on the structure, the stability, and the anion-exchange capacity
of four different LDH systems containing either nitrate, carbonate,
or oxalate as potential corrosion inhibiting agents or chloride as
a corrosion initiator. To quantify the structural change, we studied
the atom density distribution, radial distribution function, and orientation
of the intercalated anions. Additionally, we determined the stability
of the LDH systems by calculating their respective hydration energies,
hydrogen-bonded network connected to the intercalated water molecules,
as well as the self-diffusion coefficients of the intercalated anions
to provide an estimate for the probability of their release after
intercalation. The obtained computational results suggest that the
hydration state of LDHs has a significant effect on their key properties
like interlayer spacing and self-diffusion coefficients of the intercalated
anions. Furthermore, we conclude from our simulation results that
a high self-diffusion coefficient which is linked to the mobility
of the intercalated anions is vital for its release via an anion-exchange
mechanism and to subsequently mitigate corrosion reactions. Furthermore,
the presented theoretical study provides a robust force field for
the computer-assisted design of further LDH-based active anticorrosion
coatings.