Huiqun Zhou

INTERLAYER STRUCTURE AND DYNAMICS OF ALKYLAMMONIUM-INTERCALATED SMECTITES WITH AND WITHOUT WATER: A MOLECULAR DYNAMICS STUDY

The structure and dynamics of alkylammonium-intercalated smectites were simulated using molecular dynamics employing the clayff-CVFF force field, the reliability of which was firstly validated for these systems. The layering behaviors of alkyl chains confirm the scenarios of the monolayer, transition and bilayer configurations for short, medium-length and long carbon tails, respectively. In the systems without water, the alkylammonium groups are all anchored firmly above the surface six-member rings through H bonds between ammonium hydrogen and surface oxygen, and the alkyl tails are a little more mobile. With water involved, some ammoniums are dragged out of the potential barriers of the six-member rings by water molecules through the strong H bonds between water oxygen and ammonium hydrogen. The intercalated water scarcely affects the basal spacing, alkyl chain layering or alkylammonium dynamics. It is also found that the systems with alkyl chains of 11 to 14 exhibit the greatest density, resulting in the extremely limited mobility of the intercalated species.

Molecular dynamics insight into the cointercalation of hexadecyltrimethyl-ammonium and acetate ions into smectites

Abstract Classical molecular dynamic simulations are performed to investigate the microscopic properties of hexadecyltrimethylammonium (HDTMA) intercalated smectites with and without the cointercalation of acetate groups. Three model smectites with distinct layer-charge characteristics are selected as the frameworks and their HDTMA intercalates correspond to the representative monolayer, bilayer, and paraffin configurations of the aliphatic chains. In the organoclays without cointercalation, all trimethylammonium headgroups of HDTMA are fixed firmly above the center of the surface six-member rings through electrostatic attractions with surface oxygen, whereas the alkyl chains are a little more mobile. It is found that the cointercalations can significantly increase the basal spacings of the pure HDTMA intercalated smectites. The distributions and mobility of the HDTMA headgroups are not affected by the acetate ions because of the overwhelming attractions coming from the clay sheets. The acetate groups are fixed by the HDTMA headgroups through ion pairing. This simulation study provides a molecular level basis to understand the effects of cointercalation on properties of organoclays.

In silico calculation of acidity constants of carbonic acid conformers.

In order to explore the aqueous acid chemistry of carbonic acid, we employ a constrained ab initio molecular dynamics (AIMD) technique to study acid dissociations of its three conformers including CC (cis-cis), CT (cis-trans), and TT (trans-trans). The simulations of reagent states reveal similar hydration characteristics for them: the hydroxyls donate H-bonds to solvating waters but no obvious H-bonding exists between hydroxyl oxygen atoms and waters. It is found that the CC conformer dissociates spontaneously to bicarbonate within picoseconds whereas the other two can stay for relatively long simulation times. This suggests that CC has the strongest acidity among the three conformers and it is not stable in water. The simulations indicate that the symmetrical hydroxyls of TT conformer have a pKa value of 3.11 and the two asymmetrical hydroxyls of CT show different pKa values: 2.60 and 3.75, respectively. Overall, these results confirm the recent experimental measurement: about 4.0 for deuterated carbonic acid. By analyzing the dissociation processes, it is revealed that the differences of the acid constants stem from the initial steps of hydroxyls stretches. This simulation study provides a quantitative and microscopic basis for better understanding the reactivity of aqueous carbonate species.

Temperature-Dependent Phase Transition and Desorption Free Energy of Sodium Dodecyl Sulfate at the Water/Vapor Interface: Approaches from Molecular Dynamics Simulations

Adsorption of surfactants at the water/vapor interface depends upon their chemical potential at the interface, which is generally temperature-dependent. Molecular dynamics simulations have been performed to reveal temperature influences on the microstructure of sodium dodecyl sulfate (SDS) molecule adsorption layer. At room temperature, SDS molecules aggregate at the interface, being in a liquid-expanded phase, whereas they tend to spread out and probably transit to a gaseous phase as the temperature increases to above 318 K. This phase transition has been confirmed by the temperature-dependent changes in two-dimensional array, tilt angles, and immersion depths to the aqueous phase of SDS molecules. The aggregation of SDS molecules accompanies with larger immersion depths, more coordination of Na(+) ions, and less coordination of water. Desorption free energy profiles show that higher desorption free energy appears for SDS molecules at the aggregate state at low temperatures, but no energy barrier is observed. The shapes of desorption free energy profiles depend upon the distribution of SDS at the interface, which, in turn, is related to the phase state of SDS. Our study sheds light on the development of adsorption thermodynamics and kinetics theories.

Parallel Branch-Cut Algorithm Based on Simulated Annealing for Large-Scale Phase Unwrapping

Two-dimensional phase unwrapping is a key step in the phase extraction process, an image-processing stage that is common to many different systems. Many varied approaches have been proposed over the past several decades. However, with the growth of image scale, it poses new challenges in terms of computational and memory requirements to phase unwrapping that require a global approach to obtain good results. Owing to only a single process used in most previous algorithm implementations, it becomes more problematic to unwrapping when the required computing resources exceed the capability of one computer. Meanwhile, with the development and application of supercomputer techniques, high-performance computing is emerging as a promising platform for scientific applications. In this paper, a novel hybrid multiprocessing and multithreading algorithm is proposed in order to overcome the problem of unwrapping large data sets. In this algorithm, we improve on Goldsteins branch-cut algorithm using simulated annealing idea to further optimize the set of branch cuts in parallel. For large data sets, the tiling strategy based on the nature of parallel computing guarantees the globality of phase unwrapping and avoids large-scale errors introduced. Using real and simulated interferometric data, we demonstrate that our algorithms are highly competitive with other existing algorithms in speed and accuracy. We also demonstrate that the proposed algorithm can be efficiently parallelized and performed across nodes in a high-performance computing cluster.

Atomistic simulation on mixing thermodynamics of calcite-smithsonite solid solutions

Abstract By using atomistic simulation and configurational statistics techniques, the thermodynamics of mixing for calcite-smithsonite solid solutions have been investigated. By employing a 2 × 2 × 1 supercell, the configuration with the lowest energy for the solid solution with a certain composition was determined. The incorporated Zn2+ tends to occur at the sites neighboring to another substituted Zn2+ within the (0001) layer, but the substituted layers are preferentially segregated by calcite layers, and vice versa. The supercells with compositions around the two end-members stand positive enthalpies at any temperatures, whereas those supercells with composition of about Ca0.5Zn0.5CO3 prominently exhibit negative values in various temperatures of reality (e.g., <1000 K). The free energies are prominently negative at high temperatures (>1500 K) for the whole range of compositions, only those around both end-members have positive values at some low temperatures (<1200 K). In the derived phase relations of this solid solution system, the potential incorporation content of ZnCO3 into calcite is only 0-2.5% mole fraction (i.e., Zn content of 0-1.6 wt%) in most geochemistry equilibrium processes, and vice versa.