Studies on the Structure and Optical Properties of Different Cage Occupancy on sI Methane Hydrate by First-principle

doi:10.13883/j.issn1004-5929.202001003

Chinese Journal of Light Scattering ›› 2020, Vol. 32 ›› Issue (1) : 30-39. DOI: 10.13883/j.issn1004-5929.202001003

Theories of Light Scattering

Studies on the Structure and Optical Properties of Different Cage Occupancy on sI Methane Hydrate by First-principle

DENG Rong¹, WANG Zhao^2*, YANG Liang¹, LI Jin², YANG Zejin^3*

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To reveal the effects of different cage occupations on hydrate structure and related properties. The relaxation of the structure, electronic density of state and optical properties of the SI methane hydrates with three different configurations are calculated by first-principle, including (cI) only one large cage lacks its unique methane molecules; (cII), only one of the small cage lacks its unique methane molecule; (cIII) each cage is fully filled with methane molecules. The results show that the hydrate is most stable in the cIII due to its perfect structure, the cII is less stable, whereas the cI is least stable owing to its larger structural distortion after the loss of methane. On the contrary, loss of a methane molecule from cII causes negligible deformation. The relative change in cell volume is 0.56% and 2.1%, corresponding to the cII and the cI, respectively. The electronic density of states and the energy band gap of the cII is almost the same with those of cIII, differing obviously with those of cI. The calculation results display that the contribution of electronic transition is small, and proton disorder is the dominant hydrate permittivity. 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 cIII, whereas the lack of one methane in the cI can cause detectable changes. These results might provide valuable reference to the industrial exploration.

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methane hydrate / cage occupancy / optical properties / the first-principle

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DENG Rong, WANG Zhao, YANG Liang, LI Jin, YANG Zejin. Studies on the Structure and Optical Properties of Different Cage Occupancy on sI Methane Hydrate by First-principle. Chinese Journal of Light Scattering. 2020, 32(1): 30-39 https://doi.org/10.13883/j.issn1004-5929.202001003

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Received	Revised	Published
2019-05-03	2020-02-25	2020-03-10
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2022-08-19

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