Structural studies of the water pentamer

Hincapié, Gina; Acelas, Nancy; Castaño, Marcela; David, Jorge; Restrepo, Albeiro

doi:10.1016/j.cplett.2011.03.084

Cited by 105 publications

(93 citation statements)

References 44 publications

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“…5, left). The stability of five-membered rings resembling those found in the gas phase [47] has also been reported by Zhang et al for water physisorption on a different substrate [46]. When the DFT configuration is subsequently re-optimised by MM, the water-water and water-surface interactions cooperate to preserve the hydrogen bond network (Fig.…”

Section: Mackinawite (001) Surfacementioning

confidence: 56%

A force field for mackinawite surface simulations in an aqueous environment

Terranova

Leeuw

2016

Theor Chem Acc

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attracted considerable experimental [4,5] and theoretical attention [6][7][8][9][10].Like pyrite [11], mackinawite (FeS) is an exceptional scavenger for heavy metals in water [12,13], while the similarity between its structural unit [14] and reactive biological clusters [15] has suggested that FeS structures could have catalysed the formation of the first prebiotic molecules in deep sea hydrothermal vents [16,17]. However, contrary to FeS 2 , the interface between water and FeS has not been widely investigated [18,19], in part because of the lack of force field parameters for the system.In previous work, we have derived a force field, based on pairwise interactions, for molecular mechanics (MM) simulations of mackinawite [20]. In this model, each interaction can be written as a function of the interatomic distances r ij :where A, ρ, and C are the coefficients of Buckingham potentials, and q i the electrostatic charges of the atoms. In addition, to take into account polarisability effects, each sulphur atom is represented by a core and a massless shell (S-S shell ), which interact through a harmonic potential [21]:where k s is the shell force constant, and r ij the core-shell distance. The parameters, reported in Table 1, have highlighted the stability of the (001) surface compared to all other surfaces, in agreement with ab initio calculations [22] and experimental findings [23].Here, we expand the FeS interatomic potential model to include its interaction with water, the latter described byAbstract We introduce a force field for the description of the mackinawite/water interface, which we derive by refining, and consistently merging with the SPC/Fw model of water, a set of existing interatomic potentials for the mineral. The thermal behaviour predicted for bulk mackinawite is in good agreement with experiment. The adsorption of water on the low-index surfaces of mackinawite reproduces results from density functional theory calculations at different water coverages, while the behaviour of water intercalated into the mineral is also remarkably similar to that from ab initio results. The force field is therefore suitable to model bulk mackinawite and its surfaces in an aqueous environment.

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Section: Mackinawite (001) Surfacementioning

confidence: 56%

A force field for mackinawite surface simulations in an aqueous environment

Terranova

Leeuw

2016

Theor Chem Acc

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“…These results are in excellent agreement with earlier works that suggest that [r X···Y , ρ(r c )] correlations are expected for all types of binary interactions, regardless of the origin and magnitudes of individual contributions from molecular orbitals to the given contact. 27,45,46 Also notice that these exponential relationships are useful in characterizing the relative strength of the interactions, 47 as it is clearly seen that smaller concentrations of electron densities in the interaction regions lead to weaker hydrogen bonds. (b) The Laplacian of the electron density, ∇ 2 ρ(r c ), measures local concentration or depletion of charge.…”

Section: Inorganic Chemistrymentioning

confidence: 98%

Adsorption of Nitrate and Bicarbonate on Fe-(Hydr)oxide

et al. 2017

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In this work, we used density functional theory calculations to study the resulting complexes of adsorption and of inner- and outer-sphere adsorption-like of bicarbonate and nitrate over Fe-(hydr)oxide surfaces using acidic, neutral, and basic simulated pH conditions. High-spin states that follow the 5N + 1 (N is the number of Fe atoms, each having five unpaired electrons) rule are preferred. Monodentate mononuclear (MM) surface complexes are shown to lead to the most favorable thermodynamic adsorption for both bicarbonate and nitrate with -63.91 and -28.25 kJ/mol, respectively, under neutral conditions. Our results suggest that four types of regular and charged-assisted hydrogen bonds are involved in the adsorption process; all of them can be classified as closed-shell (long-range or ionic). The formal charges induce unusually short and strong hydrogen bonds. The ability of high multiplicity states of Fe clusters to adsorb oxyanions in solvated environments arises from orbital interactions: the 4s virtual orbitals in Fe have a large affinity for the 2p-type electron pairs of oxygens.

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“…Wales and Walsh 165 performed a rearrangement analysis of the C 1 global minimum similar to the trimer and found analogous rearrangement processes including the single flip and bifurcation mechanisms. A number of higher lying pentamer conformations have been identified on MP2 PESs including some three-dimensional hydrogen-bonding networks, 170,171 and three minima have been found to lie within 1.2 kcal mol −1 of the global minimum according to CCSD(T)/aTZ energies.…”

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confidence: 99%

Wavefunction methods for the accurate characterization of water clusters

Howard

Tschumper

2013

WIREs Comput Mol Sci

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Although the first ab initio Hartree-Fock computations of the water dimer were reported more than four decades ago, the detailed characterization of water clusters with sophisticated electronic structure techniques remains an important and vibrant area of research. The field of computational quantum chemistry has made significant advances since those pioneering studies. Geometry optimizations of the water dimer can now be carried out at the CCSDTQ level, and CCSD(T) energies can be computed with the aug-cc-pVTZ basis for clusters as large as (H 2 O) 17 . Some of these high-level studies are starting to reveal that the electronic structure is harder to describe for some hydrogen bonds than others. For example, discrepancies between MP2 and CCSD(T) energetics tend to increase when there are qualitative differences in the hydrogen-bonding networks of the water clusters being studied. This review highlights the recent and exciting work in this area and provides an overview of popular strategies for generating reliable properties and benchmark quality energetics for water clusters with correlated wavefunction methods. C 2013 John Wiley & Sons, Ltd.

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Structural studies of the water pentamer

Cited by 105 publications

References 44 publications

A force field for mackinawite surface simulations in an aqueous environment

A force field for mackinawite surface simulations in an aqueous environment

Adsorption of Nitrate and Bicarbonate on Fe-(Hydr)oxide

Wavefunction methods for the accurate characterization of water clusters

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