Theoretical and computational studies of the interactions between small nanoparticles and with aqueous environments

Interactions between nanoparticles (metallic, biological or a hybrid mix of the two) in aqueous solutions can have multiple biological applications. In some of them their tendency towards aggregation can be desirable (e.g. self-assembly), while in others it may impact negatively on their reliability (e.g. drug delivery). A realistic model of these systems contains about a million or more degrees of freedom, but their study has become feasible with today's high performance computing. In particular, nanoparticles of a few nanometers in size interacting at sub-nanometer distances have become a novel area of research.;The standard mean-field model of colloid science, the Derjaguin-Landau-Verwey-Overbeak (DLVO) theory, and even the extended version (XDLVO) have encountered multiple challenges when attempting to understand the interactions of small nanoparticles in the short range, since assumptions of continuous effects no longer apply. Because the region of the interaction is in the angstrom scale, the effects of atomic finite sizes and unique entropic interactions cannot be described through simple analytical formulae corresponding to generalized interaction potentials.;In this work, all-atom molecular dynamics simulations have been performed on small nanoparticles in order to provide a theoretical background for their interactions with various liquid environments as well as with each other. Such interactions have been quantified and visualized as the processes occur. Potentials of mean force have been computed as functions of the separation distances in order to obtain the binding affinities. The atomistic details of how a nanoparticle interacts with its aqueous environments and with another nanoparticle have been understood for various ligands and aqueous solutions.