Hydrogen Bond Cooperativity and the Three‐Dimensional Structures of Water Nonamers and Decamers

Pérez, Cristóbal; Zaleski, Daniel P.; Seifert, Nathan A.; Temelso, Berhane; Shields, George C.; Kisiel, Zbigniew; Pate, Brooks H.

doi:10.1002/anie.201407447

Cited by 115 publications

(122 citation statements)

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“…The D2 and D3 versions of the dispersion-corrected density functional theory within the framework of the Becke-Johnson damping function [3,38] further denoted as GD2 and GD3BJ, were employed. The following functionals were selected: B3LYP-GD3BJ, [3,10,39] B2PLYP [40], B2PLYP-GD2, B2PLYP-GD3BJ, ωB97XD and LC-ωPBE-GD3BJ [41,42,43] in combination with the Pople's 6-31++G(d,p), 6-311++G(d,p), 6-311++G(2d,2p), and the Dunning's aug-cc-pVDZ and aug-cc-pVTZ basis sets, further referred to as Pop1, Pop2, Pop3, aVDZ and aVTZ, respectively. The CCSD(T)-F12/aVDZ method was selected as a reference method, and MP2/aVDZ as well as MP2/aVTZ calculations were also carried out.…”

Section: Methods Calibrationmentioning

confidence: 99%

“…For instance, hydrated species in which small water clusters are attached to a solute, were characterized for several systems [2,10,11,12]. In a combined force-field and DFT approach, a clear segregation between the water molecules and the solute in hydrated complexes of 2-aminooxazole containing one to twenty water molecules has been reported by Calvo et al [13] The authors underlined that the solute-solvent hydrogen bonding strength is weaker than the water-water ones, leading to a negligible distortion of the water cluster up to 2-aminooxazole:(H 2 O) 15 cluster.…”

Section: Introductionmentioning

confidence: 99%

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A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

2017

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Encapsulation of small (bio-)organic molecules within water cages is governed by a subtle equilibrium between water-water and water-solute interactions. The competition between the formation of exohedral and endohedral complexes is investigated. The first step prior to a theoretical characterization of interactions involved in such complexes lies in the judicious choice of a level of theory. The β-propiolactone (BPL), a solute for which the micro-hydration was recently characterized by means of high resolution microwave spectroscopy (Angew. Chem. 2015, 127, 993), was selected for the present study, and a calibration step is carried out. It is shown that the dispersion-corrected density functional theory (DFT-D) suitably reproduce the geometric, energetic and spectroscopic features of the BPL:(H 2 O) 1-5 complexes. The experimentally-deduced structures of the BPL:(H 2 O) 4,5 species are fully understood in terms of the maximization of interactions between complementary sites in the MESPs. DFT-D calculations followed by the topological analysis within the Quantum Theory of Atoms in Molecules framework have shown that the solute could efficiently interact with (H 2 O) 6,10 clusters in a similar manner that the (H 2 O) 4,5 clusters do. The interaction of the solute with two larger water clusters is further investigated. The exohedral and endohedral BPL:(H 2 O) 20 isomers are close in energy with each other, whereas the formation of an inclusion complex is energetically more favored than the facial interaction in the case of the BPL:(H 2 O) 24 cluster. The topological analysis suggests that the substantial energetic stability is due to interactions between the solute and almost all oxygen atoms of the water cage.

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Section: Methods Calibrationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

2017

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“…The cluster dynamics can be probed by high-resolution rovibrational spectroscopy (1)(2)(3)(4)(5)(6)(7)(8)(9) and interpreted by theoretical simulations (10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27). The nature of the interactions between the water molecules is the same in the clusters as in the bulk (many-body forces beyond the three-body term are relatively weak) (28), and hence the cluster spectra can be used to test universal models (25,(29)(30)(31)(32) of the water intermolecular potential energy surface, giving insight into hydrogen bonding in all phases of water.…”

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confidence: 99%

Concerted hydrogen-bond breaking by quantum tunneling in the water hexamer prism

Richardson

Pérez

Lobsiger

et al. 2016

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Citation for published item:ihrdsonD teremy yF nd ¡ erezD grist¡ ol nd vosigerD imon nd eidD edm eF nd emelsoD ferhne nd hieldsD qeorge gF nd uisielD igniew nd lesD hvid tF nd teD frooks rF nd elthorpeD turt gF @PHITA 9gonerted hydrogenEond reking y quntum tunneling in the wter hexmer prismF9D ieneFD QSI @TPUWAF ppF IQIHEIQIQF Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

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“…Both theory and experiment have established that in the gas phase these HBs enable minimum-energy water clusters composed of 2-10 waters. [17][18][19][20] However, it is clear from many simulations that these structures do not persist in room temperature liquid water. The prevailing picture is that in the liquid phase water possesses primarily tetrahedral structure, 21,22 however a more controversial interpretation from X-ray absorption spectroscopy (XAS) and non-resonant X-ray Raman scattering (XRS) is that chains and rings are more dominant than cages.…”

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confidence: 99%

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

et al. 2017

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Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry. AbstractOn planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapor and droplets fill the lower atmosphere; even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy, and computer modeling. More recently however, supramolecular chemistry -with its expertise in macrocyclic synthesis and measuring supramolecular interactions -have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offers to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups. 4Water is ubiquitous and essential to life on planet Earth. A full understanding of aqueous solutions is therefore of significance to a wide range of fields within the atmospheric, environmental, biological and geological sciences. Within the chemical sciences, a deeper appreciation of how non-covalent interactions and chemical transformations are influenced by water would benefit a variety of fields. However, as we highlight here, there are many open questions regarding the chemical and physical properties of aqueous solutions.The aqueous realm is frequently bifurcated into the Hofmeister and hydrophobic effects, phenomena that respectively deal with the properties of solutions of salts and relatively nonpolar molecules. However, it is becoming increasingly evident that these areas do in fact frequently overlap; two prime examples being the accumulation of large polarizable anions at the air-water interface, 1-5 and the favorable interactions of polarizable anions with non-polar surfaces. [6][7][8][9][10][11][12][13][14][15] Thus the hydrophobic and Hofmeister effects are but part of a greater continuum of aqueous supramolecular chemistry, with many important and outstanding questions regarding the influence of the different kinds of non-covalent interactions involved.Studies of water and aqueous solutions have mostly been driven by the physical sciences community, a broad range of scientists whose expertise in spectroscopy, computer modeling, and biochemistry (to name just three areas) has generally not involved macrocycles or host molecules in general. However, for some time now, supramolecular chemists -with their expertise in macrocyclic synthesis and measuring weak non-covalent interactions -have been travelling a parallel course of exploration. This Review, inspired by discussions between sixteen members of each community at a recent workshop, 16 is an attempt to summarize what we know about aqueous solutions, what we do not know about them, and where the two communit...

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Hydrogen Bond Cooperativity and the Three‐Dimensional Structures of Water Nonamers and Decamers

Cited by 115 publications

References 30 publications

A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

Concerted hydrogen-bond breaking by quantum tunneling in the water hexamer prism

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

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