Theoretical investigations of CH4, C2H6, CO2 and N2 guest molecules into a dodecahedron water cluster cavities

Lebsir, Fouad; Bouyacoub, Abdelatif; Bormann, D.; Krallafa, A.

doi:10.1016/j.theochem.2008.05.037

Cited by 14 publications

(16 citation statements)

References 19 publications

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“…This seems to be close to the MP2/CBS value, partially because of the error cancellation. However, Lebsir et al[8] obtained a E vdW value of 1.79 kcal/mol using HF/6‐31G(d) method, which seriously underestimates the vdW interaction between CH 4 molecule and (H 2 O) 20 . Obviously, this is because the electron correlation effects are entirely ignored by HF method.…”

Section: Resultsmentioning

confidence: 99%

“…[7] Lebsir et al investigated the (H 2 O) 20 cage clusters with and without the presence of guest molecules at the HF/6‐31G* level of theory. [8] Recently, Loboda et al[9] examined the stabilities of empty and methane encapsulated dodecahedral (H 2 O) 20 clusters at B3LYP/3‐21G; Geng et al[10] calculated the stabilization energy of small and large water cavities occupied by CH 4 and CO 2 guests at B3LYP/6‐31G(d,p) level, while Siuda and Sadlej[11] computed the nuclear magnetic resonance parameters for methane molecule trapped in 5 12 and 5 12 6 8 water cages using B3LYP functional with the basis set aug‐cc‐pVDZ (optimization) and HuzIII‐su3 (NMR parameters). However, due to the lack of long‐range correlation, the conventional density functional theory (DFT; or HF) methods are usually insufficient to describe the noncovalent interactions in those encapsulated water cages.…”

Section: Introductionmentioning

confidence: 99%

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Appropriate description of intermolecular interactions in the methane hydrates: An assessment of DFT methods

et al. 2012

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Accurate description of hydrogen-bonding energies between water molecules and van der Waals interactions between guest molecules and host water cages is crucial for study of methane hydrates (MHs). Using high-level ab initio MP2 and CCSD(T) results as the reference, we carefully assessed the performance of a variety of exchange-correlation functionals and various basis sets in describing the noncovalent interactions in MH. The functionals under investigation include the conventional GGA, meta-GGA, and hybrid functionals (PBE, PW91, TPSS, TPSSh, B3LYP, and X3LYP), long-range corrected functionals (ωB97X, ωB97, LC-ωPBE, CAM-B3LYP, and LC-TPSS), the newly developed Minnesota class functionals (M06-L, M06-HF, M06, and M06-2X), and the dispersion-corrected density functional theory (DFT) (DFT-D) methods (B97-D, ωB97X-D, PBE-TS, PBE-Grimme, and PW91-OBS). We found that the conventional functionals are not suitable for MH, notably, the widely used B3LYP functional even predicts repulsive interaction between CH(4) and (H(2)O)(6) cluster. M06-2X is the best among the M06-Class functionals. The ωB97X-D outperforms the other DFT-D methods and is recommended for accurate first-principles calculations of MH. B97-D is also acceptable as a compromise of computational cost and precision. Considering both accuracy and efficiency, B97-D, ωB97X-D, and M06-2X functional with 6-311++G(2d,2p) basis set without basis set superposition error (BSSE) correction are recommended. Though a fairly large basis set (e.g., aug-cc-pVTZ) and BSSE correction are necessary for a reliable MP2 calculation, DFT methods are less sensitive to the basis set and BSSE correction if the basis set is sufficient (e.g., 6-311++G(2d,2p)). These assessments provide useful guidance for choosing appropriate methodology of first-principles simulation of MH and related systems. © 2012 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Appropriate description of intermolecular interactions in the methane hydrates: An assessment of DFT methods

et al. 2012

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“…21 In addition to the vibrational properties, many first-principles studies have been devoted to gas hydrates, mainly focusing on the host−guest interaction. For instance, both Lebsir 22 and Khan 23 performed ab initio calculations on the regular and irregular dodecahedron water clusters of (H 2 O) 20 with and without the presence of guest molecules. They found that incorporating a guest molecule in the (H 2 O) 20 cage could provide a better stabilization for the irregular dodecahedron (4 3 5 6 6 3 ) cage.…”

Section: Introductionmentioning

confidence: 99%

Storage Capacity and Vibration Frequencies of Guest Molecules in CH₄ and CO₂ Hydrates by First-Principles Calculations

Cao

Liu

et al. 2013

J. Phys. Chem. A

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Using first-principle calculations at B97-D/6-311++G(2d,2p) level, we systematically explore the gas capacity of five standard water cavities (5(12), 4(3)5(6)6(3), 5(12)6(2), 5(12)6(4), and 5(12)6(8)) in clathrate hydrate and study the inclusion complexes to infer general trends in vibrational frequencies of guest molecules as a function of cage size and number of guest molecules. In addition, the Raman spectra of hydrates from CO2/CH4 gases are simulated. From our calculations, the maximum cage occupancy of the five considered cages (5(12), 4(3)5(6)6(3), 5(12)6(2), 5(12)6(4), and 5(12)6(8)) is one, one, two, three, and seven for both CH4 and CO2 guest molecules, respectively. Meanwhile, the optimum cage occupancy are one, one, one, two, and four for CO2 molecules and one, one, two, three, and five for CH4 molecules, respectively. Both the C-H stretching frequency of CH4 and the C-O stretching frequency of CO2 gradually decrease as size of the water cages increases. Meanwhile, the C-H stretching frequency gradually increases as the amount of CH4 molecules in the water cavity (e.g., 5(12)6(8)) increases.

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“…1. The initial coordinates of the O atoms were taken from previous studies, 36,[44][45][46] however, some of the H atoms are oriented differently.…”

Section: Methodsmentioning

confidence: 99%

“…Their results showed that ab initio quantum chemical methods provide independent and accurate means of reaching a good understanding of the nature of hydrates and their host-guest interactions. [34][35][36] The HF method is somewhat less accurate, while MP2 is more expensive for larger molecules and tends to overestimate noncovalent interactions. More accurate and economical methods that correctly describe noncovalent interactions are therefore required.…”

Section: Introductionmentioning

confidence: 99%

Confinement of hydrogen and hydroxyl radicals in water cages: a density functional theory study

Liu

Mao

et al. 2017

RSC Adv.

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Theoretical investigations of CH4, C2H6, CO2 and N2 guest molecules into a dodecahedron water cluster cavities

Cited by 14 publications

References 19 publications

Appropriate description of intermolecular interactions in the methane hydrates: An assessment of DFT methods

Appropriate description of intermolecular interactions in the methane hydrates: An assessment of DFT methods

Storage Capacity and Vibration Frequencies of Guest Molecules in CH₄ and CO₂ Hydrates by First-Principles Calculations

Confinement of hydrogen and hydroxyl radicals in water cages: a density functional theory study

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Theoretical investigations of CH4, C2H6, CO2 and N2 guest molecules into a dodecahedron water cluster cavities

Cited by 14 publications

References 19 publications

Appropriate description of intermolecular interactions in the methane hydrates: An assessment of DFT methods

Appropriate description of intermolecular interactions in the methane hydrates: An assessment of DFT methods

Storage Capacity and Vibration Frequencies of Guest Molecules in CH4 and CO2 Hydrates by First-Principles Calculations

Confinement of hydrogen and hydroxyl radicals in water cages: a density functional theory study

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Storage Capacity and Vibration Frequencies of Guest Molecules in CH₄ and CO₂ Hydrates by First-Principles Calculations