Clathrate hydrates are crystalline compounds consisting of water molecules forming cages (so-called “host”) inside of which “guest” molecules are encapsulated depending on the thermodynamic conditions of formation (systems stable at low temperature and high pressure). These icelike systems are naturally abundant on Earth and are generally expected to exist on icy celestial bodies. Carbon monoxide hydrate might be considered an important component of the carbon cycle in the solar system since CO gas is one of the predominant forms of carbon. Intriguing fundamental properties have also been reported: the CO hydrate initially forms in the sI structure (kinetically favored) and transforms into the sII structure (thermodynamically stable). Understanding and predicting the gas hydrate structural stability then become essential. The aim of this work is, thereby, to study the structural and energetic properties of the CO hydrate using density functional theory (DFT) calculations together with neutron diffraction measurements. In addition to the comparison of DFT-derived structural properties with those from experimental neutron diffraction, the originality of this work lies in the DFT-derived energy calculations performed on a complete unit cell (sI and sII) and not only by considering guest molecules confined in an isolated water cage (as usually performed for extracting the binding energies). Interestingly, an excellent agreement (within less than 1% error) is found between the measured and DFT-derived unit cell parameters by considering the Perdew-Burke-Ernzerhof (denoted PBE) functional. Moreover, a strategy is proposed for evaluating the hydrate structural stability on the basis of potential energy analysis of the total nonbonding energies (i.e., binding energy and water substructure nonbonding energy). It is found that the sII structure is the thermodynamically stable hydrate phase. In addition, increasing the CO content in the large cages has a stabilizing effect on the sII structure, while it destabilizes the sI structure. Such findings are in agreement with the recent experimental results evidencing the structural metastability of the CO hydrate.
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