Distinguish microphase-separated structures of diblock copolymers using local order parameters.

The microphase-separated structures of block copolymers are inherently highly ordered local structures, commonly characterized by differences in domain width and curvature. By focusing on diblock copolymers, we propose local order parameters (LOPs) that accurately distinguish between adjacent microphase-separated structures on the phase diagram. We used the Molecular Assembly structure Learning package for Identifying Order parameters (MALIO) to evaluate the structure classification performance of 186 candidate LOPs.

Molecular Dynamics Simulation of the Influence of Nanoscale Structure on Water Wetting and Condensation.

Recent advances in the microfabrication technology have made it possible to control surface properties at micro- and nanoscale levels. Functional surfaces drastically change wettability and condensation processes that are essential for controlling of heat transfer. However, the direct observation of condensation on micro- and nanostructure surfaces is difficult, and further understanding of the effects of the microstructure on the phase change is required.

A molecular dynamics study of guest-host hydrogen bonding in alcohol clathrate hydrates.

Clathrate hydrates are typically stabilized by suitably sized hydrophobic guest molecules. However, it has been experimentally reported that isomers of amyl-alcohol C5H11OH can be enclosed into the 5(12)6(4) cages in structure II (sII) clathrate hydrates, even though the effective radii of the molecules are larger than the van der Waals radii of the cages. To reveal the mechanism of the anomalous enclathration of hydrophilic molecules, we performed ab initio and classical molecular dynamics simulations (MD) and analyzed the structure and dynamics of a guest-host hydrogen bond for sII 3-methyl-1-butanol and structure H (sH) 2-methyl-2-butanol clathrate hydrates.

Observation of interstitial molecular hydrogen in clathrate hydrates.

The current knowledge and description of guest molecules within clathrate hydrates only accounts for occupancy within regular polyhedral water cages. Experimental measurements and simulations, examining the tert-butylamine + H2 + H2O hydrate system, now suggest that H2 can also be incorporated within hydrate crystal structures by occupying interstitial sites, that is, locations other than the interior of regular polyhedral water cages. Specifically, H2 is found within the shared heptagonal faces of the large (4(3)5(9)6(2)7(3)) cage and in cavities formed from the disruption of smaller (4(4)5(4)) water cages.

Water proton configurations in structures I, II, and H clathrate hydrate unit cells.

Position and orientation of water protons need to be specified when the molecular simulation studies are performed for clathrate hydrates. Positions of oxygen atoms in water are experimentally determined by X-ray diffraction analysis of clathrate hydrate structures, but positions of water hydrogen atoms in the lattice are disordered. This study reports a determination of the water proton coordinates in unit cell of structure I (sI), II (sII), and H (sH) clathrate hydrates that satisfy the ice rules, have the lowest potential energy configuration for the protons, and give a net zero dipole moment.

Vibrational modes of methane in the structure H clathrate hydrate from ab initio molecular dynamics simulation.

Vibrational spectra of guest molecules in clathrate hydrates are frequently measured to determine the characteristic signatures of the molecular environment and dynamical properties of guest-host interactions. Here, we present results of our study on the vibrational frequencies of methane molecules in structure H clathrate hydrates, namely, in the 5(12) and 4(3)5(6)6(3) cages, as the frequencies of stretching vibrational modes in these environments are still unclear. The vibrational spectra of methane molecules in structure H clathrate hydrate were obtained from ab initio molecular dynamics simulation and computed from Fourier transform of autocorrelation functions for each distinct vibrational mode.

Molecular vibrations of methane molecules in the structure I clathrate hydrate from ab initio molecular dynamics simulation.

Vibrational frequencies of guest molecules in clathrate hydrates reflect the molecular environment and dynamical behavior of molecules. A detailed understanding of the mechanism for the vibrational frequency changes of the guest molecules in the clathrate hydrate cages is still incomplete. In this study, molecular vibrations of methane molecules in a structure I clathrate hydrate are calculated from ab initio molecular dynamics simulation.