Fully atomistic simulations of the response of silica nanoparticle coatings to alkane solvents.

Molecular dynamics simulations are used to study the effect of passivating ligands of varying lengths grafted to a nanoparticle and placed in various alkane solvents. Average height and density profiles for methyl-terminated alkoxylsilane ligands (-O-Si(OH)(2)(CH(2))(n)CH(3), with n = 9, 17, and 35) attached to a 5-nm-diameter amorphous silica nanoparticle with coverages of between 1.0 and 3.0 chains/nm(2) are presented for explicitly modeled, short-chain hydrocarbon solvents and for implicit good and poor solvents. Three linear solvents, C(10)H(22) (decane), C(24)H(50), and C(48)H(96), and a branched solvent, squalene, were studied. An implicit poor solvent captured the effect of the longest chain length solvent at lower temperatures, while its temperature dependence was similar to that of the branched solvent squalene. In contrast, an implicit good solvent produced coating structures that were far more extended than those found in any of the explicit solvents tested and showed little dependence on temperature. Coatings equilibrated in explicit solvents were more compact in longer-chain solvents because of autophobic dewetting. Changes in the coating density profiles were more pronounced as the solvent chain length was increased from decane to C(24)H(50) than from C(24)H(50) to C(48)H(98) for all coatings. The response of coatings in squalene was not significantly different from that of the linear chain of equal mass. Significant interpenetration of the solvent chains with the brush coating was observed only for the shortest grafted chains in decane. In all cases, the methyl terminal group was not confined to the coating edge but was found throughout the entire coating volume, from the core to the outermost shell. Increasing the temperature from 300 to 500 K led to greater average brush heights, but the dependence was weak.