First-principle study on the electronic and optical properties of cavities occupancy of SI methane hydrates.

The electronic density of state and optical properties of the SI methane hydrates with three different configurations are calculated by first-principle, including (abbreviated as cI, similarly hereinafter), each cage is fully filled with only one methane molecule; (cII), only one of the small cage lacks its unique methane molecule; (cIII), only one large cage lacks its unique methane molecule. The results show that the hydrate is most stable in the cI due to its perfect structure, the cII is less stable, whereas the cIII is least stable owing to its larger structural distortion after the loss of methane. On the contrary, loss of a methane from cII causes negligible deformation. The electronic density of states and the energy band gap of the cII is almost the same with those of cI, differing obviously with those of cIII. Methane hydrate is only responsive to light in the ultraviolet region, revealing their similar properties, regardless of their structural discrepancies, or/and the different ratios of water and methane molecules, 46/8=5.75 versus 46/7=6.57. Our calculations demonstrate that the lack of one methane in the cII causes negligible influence to the lattice structure and therefore to the electronic and optical properties in comparison with the cI, whereas the lack of one methane in the cIII can cause detectable changes. These results might provide valuable reference to the industrial exploration.