Influence of charged nanoparticles on colloidal forces: a molecular simulation study.

We employ the grand canonical Monte Carlo simulation technique to investigate the influence of charged nanoparticles (macro-ions) on the force between colloidal objects. Specifically, the structure and osmotic pressure of a system of screened Coulomb (Yukawa) particles confined between charged planar walls are simulated. We observe osmotic pressure to oscillate with wall separation and these oscillations to correspond to changes in the number of nanoparticle layers present in the slit pore. Using the Derjaguin approximation, we estimate the overall force between a colloidal sphere and a flat surface and compare our predictions to recent atomic force microscopy (AFM) results (Tulpar, A.; Van Tassel, P. R.; Walz, J. Y. Langmuir 2006, 22, 2876-2883). In excellent agreement with experiment, we find the wavelength of the force versus distance oscillations to scale as c(nu), with c being the bulk nanoparticle concentration and nu = -0.31 +/- 0.01; that is, slightly lower in magnitude from the expected value -1/3 based on average molecule spacing. By considering an order parameter measuring the extent to which neighboring particles form hexagonal symmetry, we show structural order within confined nanoparticle systems to be significantly enhanced as compared to that of bulk systems, despite being quite insensitive to wall separation. Wavelength scaling and order parameter analysis together suggest the confined macro-ion systems to be somewhat glasslike.