Dispersion corrected RPBE studies of liquid water

Forster-Tonigold, Katrin; Groß, Axel

doi:10.1063/1.4892400

Cited by 119 publications

(107 citation statements)

References 69 publications

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“…Since the RPBE-D3 functional is known to systematically overestimate the oxygen-oxygen distance of liquid water 69,83 , the first maxima of the computed g OO (r) functions are found to be systematically shifted, by about 0.1 (or 4 %) and 0.03Å (or 1 %) at 1 bar and 10 kbar, respectively, toward larger distances compared to the experimental results.…”

Section: Resultsmentioning

confidence: 70%

Water structure and solvation of osmolytes at high hydrostatic pressure: pure water and TMAO solutions at 10 kbar versus 1 bar

Imoto

Forbert

Marx

2015

Phys. Chem. Chem. Phys.

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Trimethylamine N-oxide (TMAO) is a protecting osmolyte that stabilizes proteins against both temperature and pressure denaturation. Yet, even the solvation of TMAO itself is not well understood beyond ambient conditions. Here, using ab initio molecular dynamics, we analyze how its solvation structure changes upon compressing its ≈0.5 M aqueous solution from 1 bar to 10 kbar. The neat solvent, liquid water compressed to 10 kbar, is analyzed in detail to provide a meaningful gauge for the pressure-induced solvation changes of the solute. Pure water is shown to prefer to keep four H-bonded water molecules in a locally tetrahedral arrangement up to 10 kbar. The eye-catching shape changes of its oxygen-oxygen radial distribution function, where apparently the entire second peak is shifted into the first one, are traced back to about two more water molecules which are squeezed into the tetrahedral voids that are formed in the first shell by the H-bonded water molecules. These additional molecules increase the coordination number of pure water at 10 kbar significantly, but they are definitely not H-bonded to the central water molecule; rather they are its topological second to fourth H-bonded neighbors. The pressure response of TMAO(aq) is distinctly different, although its radial distribution functions do not change much. Under ambient conditions, the negatively charged oxygen site of the solute, which is strongly hydrophilic, predominantly accepts three H-bonds, whereas a roughly equal population of threefold and square-planar fourfold H-bonding is observed at 10 kbar. Moreover, only a negligible contribution of non-H-bonded water molecules is found in the first-shell region of TMAO even at 10 kbar, in contrast to the pressure response of water itself. In the hydrophobic region of TMAO, the solvating water molecules are found to straddle the three methyl groups at ambient pressure, which remains virtually unchanged upon compressing the solution to 10 kbar. Here, the pressure response is an increase from about 17 to 21 water molecules that solvate the methyl groups despite a sizable radial compression of the hydrophobic solvation shell.

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Section: Resultsmentioning

confidence: 70%

Water structure and solvation of osmolytes at high hydrostatic pressure: pure water and TMAO solutions at 10 kbar versus 1 bar

Imoto

Forbert

Marx

2015

Phys. Chem. Chem. Phys.

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“…Besides, the liquid nature of the electrolyte requires a proper thermodynamical sampling which is computationally rather demanding on the basis of ab initio molecular dynamics (AIMD) simulations. 3,4 Moreover, it is important to take the long range dispersion interaction into account in the description of electrode-electrolyte interfaces 8,9 as well as the electrolyte 10,11 which up to recently has usually not been considered within the conventional DFT framework. There are several attempts to address these practical difficulties by, e.g., using a thermodynamical scheme to represent the electrode potential, [12][13][14][15][16] employing implicit solvation methods, [17][18][19][20][21][22][23][24] and density functionals with van der Waals corrections.…”

Section: Introductionmentioning

confidence: 99%

Density functional theory study of the electrochemical interface between a Pt electrode and an aqueous electrolyte using an implicit solvent method

Sakong

Naderian

Mathew

et al. 2015

The Journal of Chemical Physics

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113

105

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We present a computational study of the interface of a Pt electrode and an aqueous electrolyte employing semi-empirical dispersion corrections and an implicit solvent model within first-principles calculations. The electrode potential is parametrized within the computational hydrogen electrode scheme. Using one explicit layer, we find that the most realistic interface configuration is a water bilayer in the H-up configuration. Furthermore, we focus on the contribution of the dispersion interaction and the presence of water on H, O, and OH adsorption energies. This study demonstrates that the implicit water scheme represents a computationally efficient method to take the presence of an aqueous electrolyte interface with a metal electrode into account.

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“…Hybrid functionals are not appropriate for metals [35]; hence typically the generalized gradient approximation (GGA) using the Perdew-Burke-Ernzerhof (PBE) functional [36] or its revised RPBE version [37] is used. However, PBE leads to an overstructuring of water [38], even if dispersion corrections are taken into account [39]. Yet, in a series of papers it has been shown that the RPBE functional together with the D3 dispersion correction [40] and so-called zero (D3/zero) damping functions [41] yields a rather satisfactory description of the properties of water-metal interfaces [10,34], bulk liquid water [34,42], and even water clusters and ice crystals [42].…”

Section: Computational Detailsmentioning

confidence: 99%

Water adsorption on bimetallic PtRu/Pt(111) surface alloys

et al. 2016

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One contribution to a special feature 'Liquid/ Solid interfaces: structure and dynamics from spectroscopy and simulations' . The adsorption of water on bimetallic PtRu/Pt(111) surface alloys has been studied based on periodic density functional theory calculations including dispersion corrections. The Ru atoms of the PtRu surface alloy interact more strongly with water than Pt atoms, as far as both single water molecules and ice-like hexagonal structures are concerned. Within the surface alloy layer, the lateral ligand effect reducing the local reactivity of the surface atoms with increasing Ru content is more dominant than the opposing geometric effect due to the tensile strain. The structural preference for the Ru atoms also prevails at room temperature, as ab initio molecular dynamics simulations show.

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Dispersion corrected RPBE studies of liquid water

Cited by 119 publications

References 69 publications

Water structure and solvation of osmolytes at high hydrostatic pressure: pure water and TMAO solutions at 10 kbar versus 1 bar

Water structure and solvation of osmolytes at high hydrostatic pressure: pure water and TMAO solutions at 10 kbar versus 1 bar

Density functional theory study of the electrochemical interface between a Pt electrode and an aqueous electrolyte using an implicit solvent method

Water adsorption on bimetallic PtRu/Pt(111) surface alloys

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