Communication: Evidence of halogen bonds in clathrate cages

Ochoa-Resendiz, David; Batista-Romero, Fidel A.; Hernández‐Lamoneda, Ramón

doi:10.1063/1.4966644

Cited by 17 publications

(47 citation statements)

References 31 publications

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“…The geometries for the clathrate complexes have been taken from those reported in a previous local correlation study where evidence of halogen bonding was found for the Cl

_{2}

5^{12}

cage in the global energy minimum but not in Br

_{2}

5^{12} 6^{12}

, where it appeared at a geometry which does not correspond to a total energy minimum. Using the local correlation energy partitioning analysis in this case, it was possible to establish a clear correlation with the ionic energy component and for this reason the geometry at which this component is minimum is also presented and discussed.…”

Section: Computational Detailsmentioning

confidence: 99%

“…In contrast the much larger blue‐shifts observed in bromine aqueous solutions were consistent with the formation of halogen bonding interactions . However evidence of halogen bonding in clathrate cages was strongly suggested in ab initio local correlation calculations through an energy partitioning analysis and calculation of the electronic shifts at selected geometries . In particular the role of the ionic component as indicator of halogen bonding was stressed.…”

Section: Introductionmentioning

confidence: 99%

“…[2] The nature of guest-host interactions in the case of dihalogen molecules in water clathrate cages 1 has been the subject of recent debate in both experimental [3][4][5] and theoretical studies. [6][7][8][9] The initial interpretation of the observed electronic shifts in ultraviolet and visible spectra of bromine clathrate assumed that halogen bonding could not be responsible since all the water lone-pairs are involved in hydrogen bonding of the water lattice and thus not available for halogen bonding. [3] In contrast the much larger blue-shifts observed in bromine aqueous solutions were consistent with the formation of halogen bonding interactions.…”

Section: Introductionmentioning

confidence: 99%

“…[10][11][12][13] However evidence of halogen bonding in clathrate cages was strongly suggested in ab initio local correlation calculations through an energy partitioning analysis and calculation of the electronic shifts at selected geometries. [8] In particular the role of the ionic component as indicator of halogen bonding was stressed. This was further confirmed by performing a more thorough calculation of the electronic shifts taking into account the rotational motion of the dihalogen inside the cages.…”

Section: Introductionmentioning

confidence: 99%

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Halogen Bonds in Clathrate Cages: A Real Space Perspective

et al. 2018

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In this paper we present real space analyses of the nature of the dihalogen-water cage interactions in the 5 and 5 6 clathrate cages containing chlorine and bromine, respectively. Our Quantum Theory of Atoms in Molecules and Interacting Quantum Atoms results provide strong indications that halogen bonding is present even though the lone pairs of water molecules are already engaged in hydrogen bonding interactions.

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“…The geometries for the clathrate complexes have been taken from those reported in a previous local correlation study where evidence of halogen bonding was found for the Cl

_{2}

5^{12}

cage in the global energy minimum but not in Br

_{2}

5^{12} 6^{12}

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Halogen Bonds in Clathrate Cages: A Real Space Perspective

et al. 2018

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“…A simple electrostatic model of the clathrate hydrate cage predicts a blue shift in the UV-visible spectra, which agrees with experiment. Ochoa-Resendiz, BatistaRomero, and Hernandez-Lamoneda [70] in 2016 employed ab initio calculations and natural bond order analysis to investigate Cl 2 and Br 2 guests in various clathrate hydrate host sites. The picture that emerges is that of an interaction between the lone pair of the nearest oxygen atom in the clathrate hydrate host with the sigma LUMO of the halogen dimer X 2 but only when the halogen is out of its central equilibrium position in the cage, thus allowing a significant cage-halogen interaction.…”

Section: Solidificationmentioning

confidence: 99%

Clathrate Hydrates

Lee¹,

Kenney²

2018

Solidification

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The clathrate hydrates represent a distinctive, unusual, scientifically significant, and practically important class of solid state materials. Since their discovery in the early nineteenth century, their widespread distribution in oceans and permafrost regions and their ability to trap atoms and small molecules-particularly methane and other small hydrocarbons-has led to the realization that they are simultaneously a tremendous energy source and, in the face of global warming, a potential greenhouse gas release disaster of unprecedented magnitude just waiting to happen. In the twentieth century, it was realized that solid methane clathrate hydrate could plug natural gas pipelines and disrupt oil drilling processes. On the environmental positive side, clathrate hydrates can store hydrogen and sequester carbon dioxide. A brief historical review of the formation, structure, and uses of clathrate hydrates forms the backdrop for a discussion of modern scientific investigations of these solids employing spectroscopy, structure determination methods, isotopic studies, computational-theoretical modeling, and interrogations of guest-host interactions via special guests. For example, the use of colored halogens in clathrate hydrate hosts enables UV-visible spectroscopic methods to be employed to study clathrate hydrate structure.

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