In this paper we present our results from a molecular dynamics study of n-octane liquids confined between planar bcc solid surfaces. The systems studied were wide enough to develop a bulklike region throughout the middle portion of the film and two well-separated interfaces. Our work focused on segmental dynamics and relaxation of ‘‘adsorbed’’ octane molecules. In particular, we investigated the role of architectural and dynamical features peculiar to short chain molecules (almost fixed bend angles and restricted torsional rotations) on the dynamics of ‘‘adsorbed’’ chains. We found that the relaxation of octane molecules exhibits the same qualitative trends as those observed in molecular simulations of generic ‘‘bead-spring’’ oligomer films. The most important effect is the dramatic slow down of rotational motions (up to a factor of 1000) for chains adsorbed on strongly physisorbing surfaces (adhesion energy per segment of 1–2 kT). Despite the qualitative similarities with bead-spring chains, the dynamics of realistic short hydrocarbon chains are affected much more strongly by the interfacial environment than their bead-spring counterparts. These stronger effects originate largely from the suppression of torsional angle transitions inside the extremely dense first layer (in cases of strong physisorption). The frequency of torsional transitions was found to be correlated directly with the amount of ‘‘free volume’’ available inside the crowded first layer.

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The behavior of poly(propylene imine) dendrimers at three different solution pH is investigated through molecular dynamics (MD) simulations in explicit solvent. MD simulations provide an insight into the conformational properties of dendrimers via the evaluation of their size, shape, radial density distribution, static structure factor, and scattering intensity. The size of the dendrimer increases from high solution pH to low pH. The internal structure of the dendrimer is quantified in terms of the radial atomic density profile and the terminal amine group density distribution. While the radial atomic density distribution shifts away from the core of the dendrimer with decreasing pH, a significant degree of back-folding of the outer generations is observed at high pH for higher generations of growth. Results from the structure factor and scattering intensity indicate two types of conformational transitions: (i) as a function of the solution pH, where the dendrimer evolves from an expanded structure at low pH to a highly compact one at high pH (except for higher generations), and (ii) with increasing generations, where the open structure of the dendrimer at lower generations transforms to a compact structure at higher generations at both high and low pH, characterized by a change in the fractal dimension.

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The dilute solution dynamics of poly(propylene imine) (PPI) dendrimers is investigated at three different solution pH through molecular dynamics (MD) simulations. The dynamics of PPI dendrimers is characterized by both global and local relaxations that occur at different time and length scales. While the global dynamics may be described in terms of rotational diffusion, the local motion may be characterized through orientational relaxation dynamics measured in terms of the time autocorrelation function (ACF), second-order orientational ACF, and the spin− lattice relaxation rate. The global motion of dendrimers decreases with an increase in the size from high pH to low pH with increasing generations of growth. The results reveal that the segments at low pH relax faster than those at high pH, and the local mobility of the segments near the periphery is higher than the core segments. This observation is also evident from the spectral density and spin−lattice relaxation rate. High values of the spectral density at higher frequencies imply higher segmental mobility of the dendrimer at low pH relative to that at high pH. A shift in the maximum of the spin−lattice relaxation rate toward lower frequencies with decreasing generations indicates the dependence of local mobility on the topological distance of the segment from the periphery at all pH conditions.