Water hexamer clusters: Structures, energies, and predicted mid-infrared spectra

Losada, Martin; Leutwyler, Samuel

doi:10.1063/1.1487371

Cited by 103 publications

(112 citation statements)

References 58 publications

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“…However, for the water hexamer it should be noted that the energy differences between planar and non-planar structures are very small (a few kJ mol À1 ), and both structures are often given as results of the quantum calculations. [50,51] A similar conclusion is also obtained herein for the water hexamer in the gas phase using our DFT approach. As a consequence, the clear preference for a non-planar structure when the water hexamer is adsorbed (Figures 4 and 5) might be related to a small repulsion effect of the underlying p-conjugated system.…”

Section: Adsorption Of Small Water Aggregates On the Oxidized Nanoparsupporting

confidence: 84%

“…But it is well known that water pentamers and hexamers (n = 5 and n = 6) adopt planar structures when they are formed in the gas phase as shown by ab initio calculations (see Figure 5 for the optimized geometry of the gas phase pentamer found in this work, and for instance refs. [50,51] for other quantum calculations). However, for the water hexamer it should be noted that the energy differences between planar and non-planar structures are very small (a few kJ mol À1 ), and both structures are often given as results of the quantum calculations.…”

Section: Adsorption Of Small Water Aggregates On the Oxidized Nanoparmentioning

confidence: 99%

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Water Adsorption on Oxidized Single Atomic Vacancies Present at the Surface of Small Carbonaceous Nanoparticles Modeling Soot

et al. 2010

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Quantum calculations are used to study the interaction of water molecules with carbonaceous clusters containing one single carbon atom vacancy. This is a simple but realistic way to model the active surfaces found in soot emitted by aircrafts. Prior to water adsorption, the atomic vacancy is oxidised by an approaching oxygen molecule, which is also likely to occur behind planes. The results of the calculations show that this oxidation process results in the formation of one ketone-like site and one epoxide-like site around the atomic vacancy. These sites may act as nucleation centers for water molecules, which are, however, physisorbed on the oxidized surface, leading to very weak charge transfer with the surface. Although less attractive for water than, for instance, a carboxyl-like site, the ketone-like site can also participate in the hydrophilic behavior of soot primary particles. In contrast, the epoxide-like site formed around the vacancy shows a very low affinity for water molecules.

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Section: Adsorption Of Small Water Aggregates On the Oxidized Nanoparsupporting

confidence: 84%

Section: Adsorption Of Small Water Aggregates On the Oxidized Nanoparmentioning

confidence: 99%

Water Adsorption on Oxidized Single Atomic Vacancies Present at the Surface of Small Carbonaceous Nanoparticles Modeling Soot

et al. 2010

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“…We should caution that these zero-point energies and entropic effects are derived using a harmonic normal-mode analysis which may not account for certain "flipping" vibrations in the water hexamer. 36 We find that the cage structure is always less stable and is generally close in energy to the prism.…”

Section: Water Hexamermentioning

confidence: 90%

Accurate Energies and Structures for Large Water Clusters Using the X3LYP Hybrid Density Functional

2004

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We predict structures and energies of water clusters containing up to 19 waters with X3LYP, an extended hybrid density functional designed to describe noncovalently bound systems as accurately as covalent systems. Our work establishes X3LYP as the most practical ab initio method today for calculating accurate water cluster structures and energies. We compare X3LYP/aug-cc-pVTZ energies to the most accurate theoretical values available (n ) 2-6, 8), MP2 with basis set superposition error (BSSE) corrections extrapolated to the complete basis set limit. Our energies match these reference energies remarkably well, with a root-meansquare difference of 0.1 kcal/mol/water. X3LYP also has ten times less BSSE than MP2 with similar basis sets, allowing one to neglect BSSE at moderate basis sizes. The net result is that X3LYP is ∼100 times faster than canonical MP2 for moderately sized water clusters.

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“…Losada and Leutwyler [43] pointed out that the reliability of CP-corrected binding energies is not better than that of the uncorrected energies.…”

Section: Theoretical Methodsmentioning

confidence: 98%

Structure and Dynamics of Water Confined in Dimethyl Sulfoxide

Wulf

Ludwig

2006

ChemPhysChem

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We study the structure and dynamics of hydrogen-bonded complexes of H2O/D2O and dimethyl sulfoxide (DMSO) by infrared spectroscopy, NMR spectroscopy and ab initio calculations. We find that single water molecules occur in two configurations. For one half of the water monomers both OH/OD groups form strong hydrogen bonds to DMSO molecules, whereas for the other half only one of the two OH/OD groups is hydrogen-bonded to a solvent molecule. The H-bond strength between water and DMSO is in the order of that in bulk water. NMR deuteron relaxation rates and calculated deuteron quadrupole coupling constants yield rotational correlation times of water. The molecular reorientation of water monomers in DMSO is two-and-a-half times slower than in bulk water. This result can be explained by local structure behavior.

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Water hexamer clusters: Structures, energies, and predicted mid-infrared spectra

Abstract: Structures and stabilities of small silicon clusters: Ab initio molecular-orbital calculations of Si 7 -Si 11

Cited by 103 publications

References 58 publications

Water Adsorption on Oxidized Single Atomic Vacancies Present at the Surface of Small Carbonaceous Nanoparticles Modeling Soot

Water Adsorption on Oxidized Single Atomic Vacancies Present at the Surface of Small Carbonaceous Nanoparticles Modeling Soot

Accurate Energies and Structures for Large Water Clusters Using the X3LYP Hybrid Density Functional

Structure and Dynamics of Water Confined in Dimethyl Sulfoxide

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