Multiscale simulations of ligand adsorption and exchange on gold nanoparticles.

We have developed a multiscale model that combines first-principles methods with atomistic and mesoscopic simulations to explore the molecular structures and packing density of the ligands present on the gold nanoparticle (AuNP) surface, as well as the adsorption/exchange reaction kinetics of cetyltrimethylammonium bromide (CTAB)/PEG-SH ligands on different facets of gold, namely, Au(111), Au(100), and Au(110). Our model predicts that on clean gold surfaces, CTAB adsorption is diffusion limited. Specifically, CTAB has the preferentially higher adsorption rate and coverage density on Au(100) and Au(110) surfaces, forming a more compact layer with respect to that on the Au(111) surface, which could result in greater growth of gold nanoparticles along the (111) direction. As opposed to CTAB adsorption, the exchange reaction between PEG-SH with CTAB shows no selectivity to different crystal faces, and the reaction process follows Langmuir diffusion kinetics. Kinetic analysis reveals that, in water, the exchange reaction is zeroth order with respect to the concentration of an incoming PEG-SH, indicative of a dissociative exchange mechanism. The observed rate constant decreases exponentially with the PEG-SH chain length, consistent with a diffusion process for the free PEG-SH in water. In particular, we show that the exchange efficiency increases as the chain rigidness and size of the incoming ligand and/or steric bulk of the initial protecting ligand shell are decreased. Our objectives are to provide a model to assess the kinetics and thermodynamics of the adsorption/exchange reaction process, and we expect that these findings will have important implications for routine surface characterization of AuNPs.

Interfacial Properties and Hopping Diffusion of Small Nanoparticle in Polymer/Nanoparticle Composite with Attractive Interaction on Side Group.

The diffusion dynamics of fullerene (C 60 ) in unentangled linear atactic polystyrene (PS) and polypropylene (PP) melts and the structure and dynamic properties of polymers in interface area are investigated by performing all-atom molecular dynamics simulations. The comparison of the results in two systems emphasises the influence of local interactions exerted by polymer side group on the diffusion dynamics of the nanoparticle. In the normal diffusive regime at long time scales, the displacement distribution function (DDF) follows a Gaussian distribution in PP system, indicating a normal diffusion of C 60 . However, we observe multiple peaks in the DDF curve for C 60 diffusing in PS melt, which indicates a diffusion mechanism of hopping of C 60 . The attractive interaction between C 60 and phenyl ring side groups are found to be responsible for the observed hopping diffusion. In addition, we find that the C 60 is dynamically coupled with a subsection of a tetramer on PS chain, which has a similar size with C 60 . The phenyl ring on PS chain backbone tends to have a parallel configuration in the vicinity of C 60 surface, therefore neighbouring phenyl rings can form chelation effect on the C 60 surface. Consequently, the rotational dynamics of phenyl ring and the translational diffusion of styrene monomers are found to be slowed down in this interface area. We hope our results can be helpful for understanding of the influence of the local interactions on the nanoparticle diffusion dynamics and interfacial properties in polymer/nanoparticle composites.

Accelerating electrostatic interaction calculations with graphical processing units based on new developments of Ewald method using non-uniform fast Fourier transform.

We present new algorithms to improve the performance of ENUF method (F. Hedman, A. Laaksonen, Chem. Phys. Lett. 425, 2006, 142) which is essentially Ewald summation using Non-Uniform FFT (NFFT) technique. A NearDistance algorithm is developed to extensively reduce the neighbor list size in real-space computation. In reciprocal-space computation, a new algorithm is developed for NFFT for the evaluations of electrostatic interaction energies and forces. Both real-space and reciprocal-space computations are further accelerated by using graphical processing units (GPU) with CUDA technology. Especially, the use of CUNFFT (NFFT based on CUDA) very much reduces the reciprocal-space computation. In order to reach the best performance of this method, we propose a procedure for the selection of optimal parameters with controlled accuracies. With the choice of suitable parameters, we show that our method is a good alternative to the standard Ewald method with the same computational precision but a dramatically higher computational efficiency.