Clay
minerals are ubiquitous in nature, and the manner in which
they interact with their surroundings has important industrial and
environmental implications. Consequently, a molecular-level understanding
of the adsorption of molecules on clay surfaces is crucial. In this
regard computer simulations play an important role, yet the accuracy
of widely used empirical force fields (FF) and density functional
theory (DFT) exchange-correlation functionals is often unclear in
adsorption systems dominated by weak interactions. Herein we present
results from quantum Monte Carlo (QMC) for water and methanol adsorption
on the prototypical clay kaolinite. To the best of our knowledge,
this is the first time QMC has been used to investigate adsorption
at a complex, natural surface such as a clay. As well as being valuable
in their own right, the QMC benchmarks obtained provide reference
data against which the performance of cheaper DFT methods can be tested.
Indeed using various DFT exchange-correlation functionals yields a
very broad range of adsorption energies, and it is unclear a priori which evaluation is better. QMC reveals that in
the systems considered here it is essential to account for van der
Waals (vdW) dispersion forces since this alters both the absolute
and relative adsorption energies of water and methanol. We show, via
FF simulations, that incorrect relative energies can lead to significant
changes in the interfacial densities of water and methanol solutions
at the kaolinite interface. Despite the clear improvements offered
by the vdW-corrected and the vdW-inclusive functionals, absolute adsorption
energies are often overestimated, suggesting that the treatment of
vdW forces in DFT is not yet a solved problem.