Dynamics and equation of state of hydrogen clathrate hydrate as a function of cage occupation

Inerbaev, Talgat M.; Belosludov, V. R.; Belosludov, Rodion V.; Sluiter, Marcel H. F.

doi:10.1016/j.commatsci.2005.03.022

Cited by 38 publications

(39 citation statements)

References 13 publications

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“…38 The details of this potential as well as the modelling the H 2 O-H 2 interaction are presented elsewhere. 39 The LJ potential was used for methane…”

Section: Theory and Computational Detailsmentioning

confidence: 99%

Theoretical study of hydrogen storage in binary hydrogen-methane clathrate hydrates

Belosludov

Zhdanov

Субботин

et al. 2014

Journal of Renewable and Sustainable Energy

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“…38 The details of this potential as well as the modelling the H 2 O-H 2 interaction are presented elsewhere. 39 The LJ potential was used for methane…”

Section: Theory and Computational Detailsmentioning

confidence: 99%

Theoretical study of hydrogen storage in binary hydrogen-methane clathrate hydrates

Belosludov

Zhdanov

Субботин

et al. 2014

Journal of Renewable and Sustainable Energy

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“…In addition, the encapsulated ͑H 2 ͒ n cluster was assumed to undergo rotation as a rigid body inside the host cage, while its internal vibrations were treated as uncoupled harmonic oscillators. The dynamical and thermodynamic properties of the hydrogen hydrates with different numbers of H 2 molecules in the small and the large cages have also been investigated by means of the lattice dynamics calculations, 20 in which the vibrations of both the water framework and the confined H 2 molecules were treated as a collection of harmonic oscillators. This work recognized the importance of the vibrational ZPE for the thermodynamics properties of the hydrogen hydrates, but the ZPE was computed as for a set of harmonic oscillators.…”

Section: Introductionmentioning

confidence: 99%

Quantum dynamics of small H2 and D2 clusters in the large cage of structure II clathrate hydrate: Energetics, occupancy, and vibrationally averaged cluster structures

Sebastianelli

Bačić

2008

The Journal of Chemical Physics

118

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We report diffusion Monte Carlo (DMC) calculations of the quantum translation-rotation (T-R) dynamics of one to five para-H(2) (p-H(2)) and ortho-D(2) (o-D(2)) molecules inside the large hexakaidecahedral (5(12)6(4)) cage of the structure II clathrate hydrate, which was taken to be rigid. These calculations provide a quantitative description of the size evolution of the ground-state properties, energetics, and the vibrationally averaged geometries, of small (p-H(2))(n) and (o-D(2))(n) clusters, n=1-5, in nanoconfinement. The zero-point energy (ZPE) of the T-R motions rises steeply with the cluster size, reaching 74% of the potential well depth for the caged (p-H(2))(4). At low temperatures, the rapid increase of the cluster ZPE as a function of n is the main factor that limits the occupancy of the large cage to at most four H(2) or D(2) molecules, in agreement with experiments. Our DMC results concerning the vibrationally averaged spatial distribution of four D(2) molecules, their mean distance from the cage center, the D(2)-D(2) separation, and the specific orientation and localization of the tetrahedral (D(2))(4) cluster relative to the framework of the large cage, agree very well with the low-temperature neutron diffraction experiments involving the large cage with the quadruple D(2) occupancy.

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“…3,4,9 Inconclusive results have also been reported from different theoretical studies. Patchkovskii and Tse, 2 Inerbaev et al, 10 and Sebastianelli et al 11 proposed double occupancy, while Alavi et al 7 and Papadimitriou et al 12 suggested single occupancy. On incorporating quantum corrections into the empirical potential, Alavi et al 7 carried out molecular-dynamics simulations and concluded that a number of different cage-occupancy configurations are close in configurational energy, 13 such that one may expect that, in a bulk sample, a number of these may in fact coexist.…”

Section: Introductionmentioning

confidence: 99%

Molecular-Dynamics and First-Principles Calculations of Raman Spectra and Molecular and Electronic Structure of Hydrogen Clusters in Hydrogen Clathrate Hydrate

Wang

Ripmeester

et al. 2010

J. Phys. Chem. C

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Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/jp106788uAccess and use of this website and the material on it are subject to the Terms and Conditions set forth at Molecular-dynamics and first-principles calculations of raman spectra and molecular and electronic structure of hydrogen clusters in hydrogen clathrate hydrate Wang, Jianwei; Lu, Hailong; Ripmeester, John A.; Becker, Udo http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/droits L'accès à ce site Web et l'utilisation de son contenu sont assujettis aux conditions présentées dans le site LISEZ CES CONDITIONS ATTENTIVEMENT AVANT D'UTILISER CE SITE WEB. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=cb29850d-1238-4dc1-91e7-c58be9d7fabd http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=cb29850d-1238-4dc1-91e7-c58be9d7fabd Molecular-dynamics simulations and first-principles calculations are employed to understand vibrational spectroscopy and molecular and electronic structure of the encaged hydrogen molecules in hydrogen clathrate hydrate. The molecular-dynamics simulations, using empirical potentials, are performed to generate collections of the clathrate water cages with different hydrogen occupancies. The first-principles calculations, using Density Functional Theory with B3LYP hybrid density functionals for exchange and correlation, are carried out to optimize the structures and to calculate the Raman shift and activity of the stretching mode of the encaged hydrogen molecules. The Raman spectra are computed by a weighted moving average over a number of different structural configurations for different hydrogen occupancies. The results show that experimentally observed Raman peaks around 4120-4125 cm -1 are from small cages with single H 2 occupancy and peaks around 4125-4150 cm -1 from those in the large cages with one to four H 2 molecules. The Raman peaks of hydrogen molecules in the doubly occupied small cages are expected to be around or above the gas phase frequency 4155 cm. Mol...

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Dynamics and equation of state of hydrogen clathrate hydrate as a function of cage occupation

Cited by 38 publications

References 13 publications

Theoretical study of hydrogen storage in binary hydrogen-methane clathrate hydrates

Theoretical study of hydrogen storage in binary hydrogen-methane clathrate hydrates

Quantum dynamics of small H2 and D2 clusters in the large cage of structure II clathrate hydrate: Energetics, occupancy, and vibrationally averaged cluster structures

Molecular-Dynamics and First-Principles Calculations of Raman Spectra and Molecular and Electronic Structure of Hydrogen Clusters in Hydrogen Clathrate Hydrate

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