Molecular Dynamics Study of Clathrate-like Ordering of Water in Supersaturated Methane Solution at Low Pressure.

Using molecular dynamics, the evolution of a metastable solution for "methane + water" was studied for concentrations of 3.36, 6.5, 9.45, 12.2, and 14.8 mol% methane at 270 K and 1 bar during 100 ns. We have found the intriguing behavior of the system containing over 10,000 water molecules: the formation of hydrate-like structures is observed at 6.5 and 9.45 mol% concentrations throughout the entire solution volume. This formation of "blobs" and the following amorphous hydrate were studied. The creation of a metastable methane solution through supersaturation is the key to triggering the collective process of hydrate formation under low pressure. Even the first stage (0-1 ns), before the first fluctuating cavities appear, is a collective process of H-bond network reorganization. The formation of fluctuation cavities appears before steady hydrate growth begins and is associated with a preceding uniform increase in the water molecule's tetrahedrality. Later, the constantly presented hydrate cavities become the foundation for a few independent hydrate nucleation centers, this evolution is consistent with the labile cluster and local structure hypotheses. This new mechanism of hydrogen-bond network reorganization depends on the entropy of the cavity arrangement of the guest molecules in the hydrate lattice and leads to hydrate growth.

The nano-structural inhomogeneity of dynamic hydrogen bond network of TIP4P/2005 water.

A method for studying the time dependence of the short-range molecular order of water has been proposed. In the present study, water is considered as a dynamic network between molecules at distances not exceeding 3.2 Å. The instantaneous configurations obtained with the molecular dynamics method have been sequentially analyzed. The mutual orientation of each molecule with its neighboring molecules has been studied and the interaction energy of each pair of neighbor molecules has been calculated. The majority of mutual orientation angles between molecules lie in the interval [0°; 20°]. More than 85% of the molecular pairs in each instantaneous configuration form H-bonds and the H-bond network includes all water molecules in the temperature range 233-293 K. The number of H-bonds fluctuates near the mean value and increases with decreasing temperature, and the energy of the vast majority of such bonds is much higher than the thermal energy. The interaction energy of 80% of the H-bonding molecular pairs lies in the interval [-7; -4] kcal/mol. The interaction energy of pairs that do not satisfy the H-bond angle criterion lies in the interval [-5; 4] kcal/mol; the number of such bonds does not exceed 15% and decreases with decreasing temperature. For the first time it has been found that in each instantaneous configuration the H-bond network contains built-in nanometric structural heterogeneities formed by shorter H-bonds. The fraction of molecules involved in the structural heterogeneities increases from 40% to 60% with a temperature decrease from 293 K to 233 K. Each heterogeneity has a finite lifetime and changeable structure, but they are constantly present during the entire simulation time.

Influence of N2 on Formation Conditions and Guest Distribution of Mixed CO2 + CH4 Gas Hydrates.

In this contribution, a method based on a solid solution theory of clathrate hydrate for multiple cage occupancy, host lattice relaxation, and guest-guest interactions is presented to estimate hydrate formation conditions of binary and ternary gas mixtures. We performed molecular modeling of the structure, guest distribution, and hydrate formation conditions for the CO2 + CH4 and CO2 + CH4 + N2 gas hydrates. In all considered systems with and without N2, at high and medium content of CO2 in the gas phase, we found that CO2 was more favorable in occupying clathrate hydrate cavities than CH4 or N2. The addition of N2 to the gas phase increased the ratio concentration of CO2 in comparison with the concentration of CH4 in clathrate hydrates and made gas replacement more effective. The mole fraction of CO2 in the CO2 + CH4 + N2 gas hydrate rapidly increased with the growth of its content in the gas phase, and the formation pressure of the CO2 + CH4 + N2 gas hydrate rose in comparison to the formation pressure of the CO2 + CH4 gas hydrate. The obtained results agreed with the known experimental data for simple CH4 and CO2 gas hydrates and the mixed CO2 + CH4 gas hydrate.

Ozone storage capacity in clathrate hydrates formed by O3 + O2 + N2 + CO2 gas mixtures.

Ozone storage capacity in clathrate hydrates formed from gas mixtures of O3 + O2 + N2 + CO2 was studied. It was found that in such system the amount of ozone included in the hydrate phase can be at least several times higher than for the experimentally described O3 + O2 + CO2 gas hydrates. The most promising thermobaric conditions and gas phase compositions for the formation of ozone containing hydrates from gas mixtures which include nitrogen are suggested on the basis of the obtained results.

Correction: Conceptual design of tetraazaporphyrin- and subtetraazaporphyrin-based functional nanocarbon materials: electronic structures, topologies, optical properties, and methane storage capacities.

Correction for 'Conceptual design of tetraazaporphyrin- and subtetraazaporphyrin-based functional nanocarbon materials: electronic structures, topologies, optical properties, and methane storage capacities' by Rodion V. Belosludov et al., Phys. Chem. Chem. Phys., 2016, 18, 13503-13518.

Conceptual design of tetraazaporphyrin- and subtetraazaporphyrin-based functional nanocarbon materials: electronic structures, topologies, optical properties, and methane storage capacities.

A large variety of conceptual three- and fourfold tetraazaporphyrin- and subtetraazaporphyrin-based functional 3D nanocage and nanobarrel structures have been proposed on the basis of in silico design. The designed structures differ in their sizes, topology, porosity, and conjugation properties. The stability of nanocages of Oh symmetry and nanobarrels of D4h symmetry was revealed on the basis of DFT and MD calculations, whereas their optical properties were assessed using a TDDFT approach and a long-range corrected LC-wPBE exchange-correlation functional. It was shown that the electronic structures and vertical excitation energies of the functional nanocage and nanobarrel structures could be easily tuned via their size, topology, and the presence of bridging sp(3) carbon atoms. TDDFT calculations suggest significantly lower excitation energies in fully conjugated nanocages and nanobarrels compared with systems with bridging sp(3) carbon fragments. Based on DFT and TDDFT calculations, the optical properties of the new materials can rival those of known quantum dots and are superior to those of monomeric phthalocyanines and their analogues. The methane gas adsorption properties of the new nanostructures and nanotubes generated by conversion from nanobarrels were studied using an MD simulation approach. The ability to store large quantities of methane (106-216 cm(3) (STP) cm(-3)) was observed in all cases with several compounds being close to or exceeding the DOE target of 180 cm(3) (STP) cm(-3) for material-based methane storage at a pressure of 3.5 MPa and room temperature.

Solvation Mechanism of Task-Specific Ionic Liquids in Water: A Combined Investigation Using Classical Molecular Dynamics and Density Functional Theory.

The solvation behavior of task-specific ionic liquids (TSILs) containing a common, L-histidine derived imidazolium cation [C20H28N3O3](+) and different anions, bromide-[Br](-) and bis(trifluoromethylsulfonyl)amide-[NTF2](-), in water is examined, computationally. These amino acid functionalized ionic liquids (ILs) are taken into account because of their ability to react with rare earth metal salts. It has been noted that the TSIL with [Br](-) is more soluble than its counterpart TSIL with [NTF2](-), experimentally. In this theoretical work, the combined classical molecular dynamics (CMD) and density functional theory (DFT) calculations are performed to study the behavior of the bulk phase of these two TSILs in the vicinity of water (H2O) molecules with different concentrations. Initially, all the constructed systems are equilibrated using the CMD method. The final structures of the equilibrated systems are extracted for DFT calculations. Under CMD operation, the radial distribution function (RDF) plots and viscosity of TSILs are analyzed to understand the effect of water on TSILs. In the DFT regime, binding energy per H2O, charge transfer, charge density mapping, and electronic density of states (EDOS) analyses are done. The CMD results along with the DFT results are consolidated to support the hydrophilic and hydrophobic nature of the TSILs. Interestingly, we have found a strong correlation between the viscosity and the EDOS results that leads to an understanding of the hydration properties of the TSILs.