Anti-cooperativity of the two water OH groups

Luck, W. A. P.; Klein, Dietmar; Rangsriwatananon, Kunwadee

doi:10.1016/s0022-2860(97)00055-0

Cited by 34 publications

(20 citation statements)

References 30 publications

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“…20 In the case of ASW, one of the most salient physical parameters is the cooperative effect between the H 2 O molecules. 21 In fact, not only the cooperative effects, but also the anti-cooperativity between OH groups must be considered; anti-cooperativity could also arise from polarisation by the closest H-bonds, 22 depending on the basic or acidic behaviour of the nearest neighbouring H 2 O molecules. The cooperative and anti-cooperative effects could explain the fact that some weaker H-bonds are broken upon irradiation while others reinforced by cooperative effects are not.…”

Section: Effect Of Irradiation Timementioning

confidence: 99%

Inhomogeneity of the amorphous solid water dangling bonds

Coussan

Roubin

Noble

2015

Phys. Chem. Chem. Phys.

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Amorphous solid water (ASW) is one of the most widely studied molecular systems because of its importance in the physics and chemistry of the interstellar medium and the upper layers of the Earth's atmosphere. Although the global structure of this material, i.e. the bulk and the surface, is well characterised, we are far from having an overall understanding of the changes induced upon chemical or physical perturbation. More specifically, the behaviour of the surface and the immediate sublayers upon mid-infrared irradiation must be understood due to its direct effect on the adsorption capacities of the ASW surface. Small molecules can accrete or form at the surface, adsorbed on the dangling OH groups of surface water molecules. This behaviour allows further reactivity which, in turn, could lead to more complex molecular systems. We have already demonstrated that selective IR irradiations of surface water molecules induce a modification of the surface and the production of a new monomer species which bonds to the surface via its two electronic doublets. However, we did not probe the structure of the dangling bands, namely their homogeneity or inhomogeneity. The structure and orientation of these surface molecules are closely linked to the way the surface can relax its vibrational energy. In this work, we have focussed our attention on the two dH dangling bonds, carrying out a series of selective irradiations which reveal the inhomogeneity of these surface modes. We have also studied the effects of irradiation duration on the surface reorientation, determining that the maximum photoinduced isomerisation yield is ∼15%.

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Section: Effect Of Irradiation Timementioning

confidence: 99%

Inhomogeneity of the amorphous solid water dangling bonds

Coussan

Roubin

Noble

2015

Phys. Chem. Chem. Phys.

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“…Cooperativity between water molecules is particularly important, because in liquid water at room temperature, the great majority of the molecules are hydrogen-bonded to each other, the concentration of "free" OH groups being very low [8]. For this reason, extensive theoretical calculations have been carried out on the cooperativity in water [9][10][11][12][13]. In recent works, the interaction between proton acceptors (or donors) and two (or more) water molecules has been discussed [14][15][16][17][18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of the Cooperativity in CH₃CHO·2H₂O, CH₂FCHO·2H₂O, and CH₃CFO·2H₂O Systems

Chandra

Zeegers‐Huyskens

2012

Journal of Atomic, Molecular, and Optical Physics

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The hydrogen bond interaction between CH3CHO, CH2FCHO, and CH3CFO and two water molecules is investigated at the B3LYP/6-311++G(d,p) level. The results are compared with the complexes involving the same carbonyl derivatives and one water molecule. The calculations involve the optimization of the structure, the harmonic vibrational frequencies, and relevant NBO (natural bond orbital) parameters such as the NBO charges, the occupation of antibonding orbitals, and intra- and intermolecular hyperconjugation energies. Two stable cyclic structures are predicted. The two structures are stabilized by C=O⋯HO hydrogen bond. The A structures are further stabilized by CH⋯O bond involving the CH3(CH2F) group. This bond results in an elongation of the CH bond and red shift of theν(CH) vibration. The B structures are stabilized by CH⋯O interaction involving the aldehydic CH bond. The formation of this bond results in a marked contraction of the CH bond and blue shift of theν(CH) vibration indicating the predominance of the lone pair effect in determining the CH distances. The total interaction energies range from −12.40 to −13.50 kcal mol−1. The cooperative energies calculated at the trimer geometry are comprised between −2.30 and −2.60 kcal mol−1.

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“…However, the long known concept of anticooperativity of the two hydrogen bonds donated by the same water molecule provides an explanation. 47 Namely, whenever a water molecule donates to a strong hydrogen bond, the other hydrogen is engaged in a weak hydrogen bond. This particular phenomenon has recently computationally been confirmed for PO 4 3– , for which the short and strong water–phosphate hydrogen bonds are accompanied by weak hydrogen bonds donated by the same hydrating water molecules to the second hydration shell.…”

Section: Results and Discussionmentioning

confidence: 99%

Hydration of Oxometallate Ions in Aqueous Solution

Śmiechowski

Persson

2020

Inorg. Chem.

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The strength of hydrogen bonding to and structure of hydrated oxometallate ions in aqueous solution have been studied by double difference infrared (DDIR) spectroscopy and large-angle X-ray scattering (LAXS), respectively. Anions are hydrated by accepting hydrogen bonds from the hydrating water molecules. The oxygen atom of the permanganate and perrhenate ions form weaker and longer hydrogen bonds to water than the hydrogen bonds in bulk water (i.e., they act as structure breakers), while the oxygen atoms of the chromate, dichromate, molybdate, tungstate, and hydrogenvanadate ions form hydrogen bonds stronger than those in bulk water (i.e., they act as structure makers). The oxometallate ions form one hydration shell distinguishable from bulk water as determined by DDIR spectroscopy and LAXS. The hydration of oxoanions results in X–O bond distances ca. 0.02 Å longer than those in unsolvated ions in the solid state not involved in strong bonding to counterions. The oxygens of oxoanions with a central atom from the second and third series in the periodic table and the hydrogenvanadate ion hydrogen bind three hydrating water molecules, while oxygens of oxoanions with a heavier central atom only form hydrogen bonds to two water molecules.

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Anti-cooperativity of the two water OH groups

Cited by 34 publications

References 30 publications

Inhomogeneity of the amorphous solid water dangling bonds

Inhomogeneity of the amorphous solid water dangling bonds

Theoretical Investigation of the Cooperativity in CH₃CHO·2H₂O, CH₂FCHO·2H₂O, and CH₃CFO·2H₂O Systems

Hydration of Oxometallate Ions in Aqueous Solution

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Anti-cooperativity of the two water OH groups

Cited by 34 publications

References 30 publications

Inhomogeneity of the amorphous solid water dangling bonds

Inhomogeneity of the amorphous solid water dangling bonds

Theoretical Investigation of the Cooperativity in CH3CHO·2H2O, CH2FCHO·2H2O, and CH3CFO·2H2O Systems

Hydration of Oxometallate Ions in Aqueous Solution

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Theoretical Investigation of the Cooperativity in CH₃CHO·2H₂O, CH₂FCHO·2H₂O, and CH₃CFO·2H₂O Systems