Date of this Version
Published in Journal of the American Chemical Society 136 (2014), pp 10661−10668. doi 10.1021/ja5041539
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.