Spontaneous Formation of One-Dimensional Hydrogen Gas Hydrate in Carbon Nanotubes

We present molecular dynamics simulation evidence of spontaneous formation of quasi-one-dimensional (Q1D) hydrogen gas hydrates within single-walled carbon nanotubes (SW-CNTs) of nanometer-sized diameter (1−1.3 nm) near ambient temperature. Contrary to conventional 3D gas hydrates in which the guest molecules are typically contained in individual and isolated cages in the host lattice, the guest H2 molecules in the Q1D gas hydrates are contained within a 1D nanochannel in which the H2 molecules form a molecule wire. In particular, we show that in the (15,0) zigzag SW-CNT, the hexagonal H2 hydrate tends to form, with one H2 molecule per hexagonal prism, while in the (16,0) zigzag SW-CNT, the heptagonal H2 hydrate tends to form, with one H2 molecule per heptagonal prism. In contrast, in the (17,0) zigzag SW-CNT, the octagonal H2 hydrate can form, with either one H2 or two H2 molecules per pentagonal prism (single or double occupancy). Interestingly, in the hexagonal or heptagonal ice nanotube, the H2 wire is solid-like as the axial diffusion constant is very low (× 10−10 cm2/s), whereas in the octagonal ice nanotube, the H2 wire is liquid-like as its axial diffusion constant is comparable to 10−5 cm2/s

Novel low dimensional silicon and water nanostructures

MD simulations of confined water and silicon were carried out to investigate liquid to solid phase transition phenomena in the confinement system. The simulations provide possible evidence of new low-dimensional polymorphs of silicon and ice. The low-dimensional structures were further examined by using ab initio methods. Two five-site potential models of water were employed to study liquid to quasitwo-dimensional solid transitions of water. The simulations of five-site models confirm our previous simulation results on basis of the four-site TIP4P model of water. Ab initio plane-wave total-energy calculation is carried out to study the relative stability of the quasi-one-dimensional (Q1D) pentagon and hexagon ice nanotubes. Electronic structure calculations indicate the two Q1D ice nanotubes have nearly the same band structures and energy bandgap as those of proton-ordered bulk ice Ih. Atomistic computer simulation evidences are also presented for possible existence of low dimensional silicon structures. The local geometric structure of low dimensional structures are different from the local tetrahedral structure of cubic diamond silicon even though the coordination number of atoms of the low-dimensional silicon allotropes is still four-fold. Ab initio calculations show that the low-dimensional silicon structures are locally stable in vacuum and have zero bandgap, suggesting that they are possibly metals rather than wide-gap semiconductors

Polymorphism and polyamorphism in bilayer water confined to slit nanopore under high pressure

A distinctive physical property of bulk water is its rich solid-state phase behavior, which includes 15 crystalline (ice I–ice XIV) and at least 3 glassy forms ofwater, namely, low-density amorphous, highdensity amorphous, and very-high-density amorphous (VHDA). Nanoscale confinement adds a new physical variable that can result in a wealth of new quasi-2D phases of ice and amorphous ice. Previous computer simulations have revealed that when water is confined between two flat hydrophobic plates about 7–9 Å apart, numerous bilayer (BL) ices (or polymorphs) can arise [e.g., BL-hexagonal ice (BL-ice I)]. Indeed, growth of the BL-ice I through vapor deposition on graphene/Pt(111) substrate has been achieved experimentally. Herein, we report computer simulation evidence of pressure- induced amorphization from BL-ice I to BL-amorphous and then to BL-VHDA2 at 250 K and 3 GPa. In particular, BL-VHDA2 can transform into BL-VHDA1 via decompression from 3 to 1.5 GPa at 250 K. This phenomenon of 2D polyamorphic transition is akin to the pressure- induced amorphization in 3D ice (e.g., from hexagonal ice to HDA and then to VHDA via isobaric annealing). Moreover, when the BL-ice I is compressed instantly to 6 GPa, a new very-high-density BL ice is formed. This new phase of BL ice can be viewed as an array of square ice nanotubes. Insights obtained from pressure-induced amorphization and crystallization of confined water offer a guide with which to seek a thermodynamic path to grow a new form of methane clathrate whose BL ice framework exhibits the Archimedean 4·82 (square-octagon) pattern

Graphene-Like Bilayer Hexagonal Silicon Polymorph

We present molecular dynamics simulation evidence for a freezing transition from liquid silicon to quasi-twodimensional (quasi-2D) bilayer silicon in a slit nanopore. This new quasi-2D polymorph of silicon exhibits a bilayer hexagonal structure in which the covalent coordination number of every silicon atom is four. Quantum molecular dynamics simulations show that the stand-alone bilayer silicon (without the confinement) is still stable at 400 K. Electronic band-structure calculations suggest that the bilayer hexagonal silicon is a quasi-2D semimetal, similar to a graphene monolayer, but with an indirect zero band gap

Guest-free monolayer clathrate and its coexistence with two-dimensional high-density ice

Three-dimensional (3D) gas clathrates are ice-like but distinguished from bulk ices by containing polyhedral nano-cages to accommodate small gas molecules. Without space filling by gas molecules, standalone 3D clathrates have not been observed to form in the laboratory, and they appear to be unstable except at negative pressure. Thus far, experimental evidence for guest‐free clathrates has only been found in germanium and silicon, although guest‐free hydrate clathrates have been found, in recent simulations, able to grow from cold stretched water, if first nucleated. Herein, we report simulation evidence of spontaneous formation of monolayer clathrate ice, with or without gas molecules, within hydrophobic nano-slit at low temperatures. The guest-free monolayer clathrate ice is a low-density ice (LDI) whose geometric pattern is identical to Archimedean 4 · 82-truncated square tiling, i.e. a mosaic of tetragons and octagons. At large positive pressure, a second phase of 2D monolayer ice, i.e. the puckered square high-density ice (HDI) can form. The triple point of the LDI/liquid/HDI three-phase coexistence resembles that of the ice-Ih∕water∕ice-III three-phase coexistence. More interestingly, when the LDI is under a strong compression at 200 K, it transforms into the HDI via a liquid intermediate state, the first direct evidence of Ostwald’s rule of stages at 2D. The tensile limit of the 2D LDI and water are close to that of bulk ice-Ih and laboratory water. Includes Supporting Information. Five movies (.mpg) are attached (below) as Related files

Melting temperature of ice \u3ci\u3eI\u3c/i\u3e\u3csub\u3e\u3ci\u3eh\u3c/i\u3e\u3c/sub\u3e calculated from coexisting solid-liquid phases

The purpose of this paper is twofold: (1) to compute the melting temperature (Tm) of ice Ih with both TIP4P and TIP5P models by using the two-phase coexistence method and to compare with previously obtained Tm; (2) to compute the Tm using recently improved TIP4P and TIP5P models, namely, the TIP4P-Ew (Ref. 6) and TIP5P-Ew (Ref. 7) models. Both models are developed specifically for use with Ewald techniques. The TIP4P-Ew model, in particular, has shown substantial improvement over the original TIP4P model as it can reproduce the density maximum at about 274 K, very close to 277 K of the real water. The original TIP5P model can reproduce the measured Tm. It will be of interest to see whether the improved TIP5P-Ew model can still hold the same level of prediction as far as the Tm is concerned

Spontaneous Formation of One-Dimensional Hydrogen Gas Hydrate in Carbon Nanotubes

We present molecular dynamics simulation evidence of spontaneous formation of quasi-one-dimensional (Q1D) hydrogen gas hydrates within single-walled carbon nanotubes (SW-CNTs) of nanometer-sized diameter (1−1.3 nm) near ambient temperature. Contrary to conventional 3D gas hydrates in which the guest molecules are typically contained in individual and isolated cages in the host lattice, the guest H2 molecules in the Q1D gas hydrates are contained within a 1D nanochannel in which the H2 molecules form a molecule wire. In particular, we show that in the (15,0) zigzag SW-CNT, the hexagonal H2 hydrate tends to form, with one H2 molecule per hexagonal prism, while in the (16,0) zigzag SW-CNT, the heptagonal H2 hydrate tends to form, with one H2 molecule per heptagonal prism. In contrast, in the (17,0) zigzag SW-CNT, the octagonal H2 hydrate can form, with either one H2 or two H2 molecules per pentagonal prism (single or double occupancy). Interestingly, in the hexagonal or heptagonal ice nanotube, the H2 wire is solid-like as the axial diffusion constant is very low (× 10−10 cm2/s), whereas in the octagonal ice nanotube, the H2 wire is liquid-like as its axial diffusion constant is comparable to 10−5 cm2/s

Multiwalled ice helixes and ice nanotubes

We report six phases of high-density nano-ice predicted to form within carbon nanotubes (CNTs) at high pressure. High-density nano-ice self-assembled within smaller-diameter CNT (17,0) exhibits a double-walled helical structure where the outer wall consists of four double-stranded helixes, which resemble a DNA double helix, and the inner wall is a quadruple-stranded helix. Four other double-walled nano-ices, self-assembled respectively in two larger-diameter CNTs (20,0 and 22,0), display tubular structure. Within CNT (24,0), the confined water can freeze spontaneously into a triple-walled helical nano-ice where the outer wall is an 18-stranded helix and the middle and inner walls are hextuple-stranded helixes

Ferroelectric hexagonal and rhombic monolayer ice phases

Two new phases of water, the mid-density hexagonal monolayer ice and the high-density flat rhombic monolayer ice, are observed in our molecular dynamics simulations of monolayer water confined between two smooth hydrophobic walls. These are in addition to the two monolayer ices reported previously, namely, the low-density 4∙82 monolayer ice and the high-density puckered rhombic monolayer ice (HD-pRMI). Stabilities of the structures are confirmed by ab initio computation. Importantly, both new phases and the HD-pRMI are predicted to be ferroelectric. An in-plane external electric field can further stabilize these ferroelectric monolayer ices

Metallic single-walled silicon nanotubes

Atomistic computer-simulation evidences are presented for the possible existence of one-dimensional silicon nanostructures: the square, pentagonal, and hexagonal single-walled silicon nanotubes (SWSNTs). The local geometric structure of the SWSNTs differs from the local tetrahedral structure of cubic diamond silicon, although the coordination number of atoms of the SWSNTs is still fourfold. Ab initio calculations show that the SWSNTs are locally stable in vacuum and have zero band gap, suggesting that the SWSNTs are possibly metals rather than wide-gap semiconductors