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Assessing Intermolecular Interactions in Guest-Free Clathrate Hydrate Systems
dataset
posted on 2018-01-12, 00:00 authored by Iván León-Merino, Raúl Rodríguez-Segundo, Daniel J. Arismendi-Arrieta, Rita ProsmitiRecently,
empty hydrate structures sI, sII, sH, and others have
been proposed as low-density ice structures by both experimental observations
and computer simulations. Some of them have been synthesized in the
laboratory, which motivates further investigations on the stability
of such guest-free clathrate structures. Using semiempirical and ab initio-based water models, as well as dispersion-corrected
density functional theory approaches, we predict their stability,
including cooperative many-body effects, in comparison with reference
data from converged wave function-based DF-MP2 electronic structure
calculations. We show that large basis sets and counterpoise corrections
are required to improve convergence in the interaction/binding energies
for such systems. Therefore, extrapolation schemes based on triple/quadruple
and quadruple/quintuple ζ quality basis sets are used to reach
high accuracy. Eleven different water structures corresponding to
dodecahedron, edge sharing, face sharing, and fused cubes, as a part
of the WATER27 database, as well as cavities from the sI, sII, and
sH clathrate hydrates formed by 20, 24, 28, and 36 water molecules,
are employed, and new benchmark energies are reported. Using these
benchmark sets of interaction energies, we assess the performance
of both analytical models and direct DFT calculations for such clathrate-like
systems. In particular, seven popular water models (TIP4P/ice, TIP4P/2005,
q-TIP4P/F, TTM2-F, TTM3-F, TTM4-F, and MB-pol) available in the literature,
and nine density functional approximations (3 meta-GGAs, 3 hybrids,
and 3 range separated functionals) are used to investigate their accuracy.
By including dispersion corrections, our results show that errors
in the interaction energies are reduced for most of the DFT functionals.
Despite the difficulties faced by current water models and DFT functionals
to accurately describe the interactions in such water systems, we
found some general trends that could serve to extend their applicability
to larger systems.
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water models36 water moleculesDFT functionalssetinteraction energiesTIP 4P TIP 4P q-TIP 4P TTM 2-F TTM 3-F TTM 4-Fguest-free clathrate structuresWATER 27 databasesH clathrate hydratesGuest-Free Clathrate Hydrate Systemswave function-based DF-MP 2Assessing Intermolecular Interactionshydrate structures sI
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