No abstract

Micellization brought about by nonclassical hydrophobic effect invokes enthalpy as the driving force. Thus, the underlying molecular phenomena differ from the entropically dominated hydrophobic effect. In quest for a molecular-scale understanding, we report on the molecular arrangement of nonamphiphilic structures of an anionic boron cluster compound, COSAN. We synergistically combine experimental (NMR and calorimetry) and theoretical (molecular dynamics and quantum chemical calculations) approaches. The experimental data support the mechanism of closed association of COSAN, where the self-assembly is driven by the enthalpy contribution to the free energy. Molecular dynamics simulations in explicit solvent show that water molecules form a patchy network around COSAN molecules, giving rise to the strong hydrophobic self-association. In the second solvation shell, water forms a slightly hydrophilic "spot" close to the C-H segments of the cluster.

Fluids of spherical colloids possessing an off-centered embedded magnetic dipole were investigated by using Monte Carlo simulations. Systems of colloids with different strengths and directions of the embedded dipole moment confined in a 2D space without and with an external magnetic field applied were considered. The fluids were characterized by radial distribution functions, angular distribution functions, cluster data, and energetic data. In the absence of an external field, the colloids form dimers and trimers at sufficiently large magnetic moment without the tendency of forming chains of colloids as appearing in systems with particles possessing a central magnetic dipole. In the presence of an external field, chains of colloids aligned in a zigzag fashion were formed for a field parallel to the plane of the particles, whereas the colloidal ordering was suppressed in the presence of a field perpendicular to that plane. The findings agree surprisingly well with the recent experimental observations on fluids containing spherical polymer colloids with embedded single-domain magnetic hematite cubes

We present an expanded Wolf formalism for direct summation of long-range dipole-dipole interactions and rule-of-thumbs how to choose optimal spherical cutoff (Rc) and damping parameter (α). This is done by comparing liquid radial distribution functions, dipole-dipole orientation correlations, particle energies, and dielectric constants, with Ewald sums and the Reaction field method. The resulting rule states that ασ < 1 and αRc > 3 for reduced densities around ρ(∗) = 1 where σ is the particle size. Being a pair potential, the presented approach scales linearly with system size and is applicable to simulations involving point dipoles such as the Stockmayer fluid and polarizable water models.