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Structural Stabilization of D- and T-Cages of the sI Hydrate by Gas Molecules

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Abstract

Mechanisms of structural stabilization of sI hydrates by CH4, H2S, H2, N2, Ar, Kr, Xe, CO2, C2H6, C3H6 gas molecules are studied by the density functional method. It is shown that the hydrate D- and T-cages are deformed and their radii are changed (up to –0.23%) upon the introduction of guest gas molecules. Binding energies of the gases in the D- and T-cages are calculated. It is established that molecules with diameters d < 5 Å and d > 5 Å stabilize better D- and T-cages, respectively. Two groups of gases can be distinguished, depending on the binding energy dependence on the molecule′s mass: molecular gases (dEb/dM ∈ (–0.008; –0.006) eV·mol/g) and atomic gases (dEb/dM ∈ (–0.002; –0.0015) eV·mol/g). It is shown that the orientation of extended CO2, C2H6, and C3H6 molecules along the long axis of the T-cage is most energetically favorable. Densities of electronic states N(E) are calculated for the unfilled sI hydrate and for sI hydrates containing CH4 and CO2. It is shown that the presence of a guest molecule decreases the energy of the electronic subsystem and increases the hydrate′s stability.

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Funding

Large-scale quantum mechanical calculations were performed on the computing cluster of the Kazan (Volga Region) Federal University.

This work was funded by the Russian Science Foundation (project No. 22-22-00508).

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Authors and Affiliations

  1. Kazan (Volga region) Federal University, Kazan, Russia

    M. B. Yunusov & R. M. Khusnutdinov

  2. Udmurt Federal Research Center, Ural Branch, Russian Academy of Sciences, Izhevsk, Russia

    R. M. Khusnutdinov

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  1. M. B. Yunusov
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Correspondence to M. B. Yunusov.

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Russian Text © The Author(s), 2023, published in Zhurnal Strukturnoi Khimii, 2023, Vol. 64, No. 4, 108770.https://doi.org/10.26902/JSC_id108770

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Yunusov, M.B., Khusnutdinov, R.M. Structural Stabilization of D- and T-Cages of the sI Hydrate by Gas Molecules. J Struct Chem 64, 584–594 (2023). https://doi.org/10.1134/S0022476623040066

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