Benchmark oxygen-oxygen pair-distribution function of ambient water from x-ray diffraction measurements with a wide <i>Q</i>-range

Skinner, Lawrie; Huang, Congcong; Schlesinger, Daniel; Pettersson, Lars G. M.; Nilsson, Anders; Benmore, C. J.

doi:10.1063/1.4790861

Cited by 456 publications

(595 citation statements)

References 46 publications

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“…The oxygen-oxygen and oxygen-hydrogen radial distribution functions (RDF) as obtained with various functionals are compared with recent experimental results [49][50][51][52] in Figs. 5 and 6, respectively.…”

Section: B Radial Distribution Functionsmentioning

confidence: 99%

Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions

Miceli

Gironcoli

Pasquarello

2015

The Journal of Chemical Physics

114

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We investigate the structural properties of liquid water at near ambient conditions using first-principles molecular dynamics simulations based on a semilocal density functional augmented with nonlocal van der Waals interactions. The adopted scheme offers the advantage of simulating liquid water at essentially the same computational cost of standard semilocal functionals. Applied to the water dimer and to ice I h , we find that the hydrogen-bond energy is only slightly enhanced compared to a standard semilocal functional. We simulate liquid water through molecular dynamics in the N pH statistical ensemble allowing for fluctuations of the system density. The structure of the liquid departs from that found with a semilocal functional leading to more compact structural arrangements. This indicates that the directionality of the hydrogenbond interaction has a diminished role as compared to the overall attractions, as expected when dispersion interactions are accounted for. This is substantiated through a detailed analysis comprising the study of the partial radial distribution functions, various local order indices, the hydrogen-bond network, and the selfdiffusion coefficient. The explicit treatment of the van der Waals interactions leads to an overall improved description of liquid water.

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Section: B Radial Distribution Functionsmentioning

confidence: 99%

Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions

Miceli

Gironcoli

Pasquarello

2015

The Journal of Chemical Physics

114

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“…The RDFs of VV10 and vdW-DF PBE are compared with a recent determination from x-ray diffraction 52 at ambient conditions (the lowest density line in Fig. 6).…”

Section: B Structural Variations With Densitymentioning

confidence: 99%

“…All simulations are performed at the same density and temperature, although with differing system sizes (see Table III). The experimental data from x-ray diffraction measurements 52 are for ambient conditions.…”

Section: Appendix A: Overview Of Simulationsmentioning

confidence: 99%

Room temperature compressibility and diffusivity of liquid water from first principles

Corsetti

Artacho

Soler

et al. 2013

The Journal of Chemical Physics

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The isothermal compressibility of water is essential to understand its anomalous properties. We compute it by ab initio molecular dynamics simulations of 200 molecules at five densities, using two different van der Waals density functionals. While both functionals predict compressibilities within ∼30% of experiment, only one of them accurately reproduces, within the uncertainty of the simulation, the density dependence of the self-diffusion coefficient in the anomalous region. The discrepancies between the two functionals are explained in terms of the low-and high-density structures of the liquid. © 2013 AIP Publishing LLC. [http://dx

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“…The D3 dispersion correction leads to a g OO (r) that is almost featureless after the first peak, such a smearing out of the The most recent experimental Oxygen-Oxygen RDF, obtained from x-ray diffraction and taken from Ref. 66 , is depicted as a solid black line.…”

mentioning

confidence: 99%

“…Experimental values taken from Ref. 66 . CN is the average coordination number calculated from the integral 4πρ n r 2 g OO (r) up to the first minimum, where ρ n is the average number density of Oxygen atoms.…”

mentioning

confidence: 99%

Bulk Liquid Water at Ambient Temperature and Pressure from MP2 Theory

Ben

Schönherr

Hutter

et al. 2013

J. Phys. Chem. Lett.

138

112

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MP2 provides a good description of hydrogen bonding in water clusters and includes longrange dispersion interactions without the need to introduce empirical elements in the description of the interatomic potential. To assess its performance for bulk liquid water under ambient conditions, an isobaric-isothermal (NpT) Monte Carlo simulation at the second-order Moller-Plesset perturbation theory level (MP2) has been performed. The obtained value of the water density is excellent (1.02 g/mL), and the calculated radial distribution functions are in fair agreement with experimental data. The MP2 results are compared to a few density functional approximations, including semilocal functionals, hybrid functionals, and functionals including empirical dispersion corrections. These results demonstrate the feasibility of directly sampling the potential energy surface of condensed-phase systems using correlated wave function theory, and their quality paves the way for further applications. Understanding the structural and electronic properties of liquid water at ambient conditions is a major challenge in condensed matter simulations. Water is a crucial ingredient for a large variety of systems of prime importance in basic chemistry, biology, and physics, as well as in the applied fields of catalysis and energy production. The water molecule has a large dipole moment and polarizability, is a multiple hydrogen donor and acceptor and can easily build network structures.The total cohesive energy in the condensed phase is, as a consequence of these properties, a sum of many weak interactions. Theoretical models face therefore the challenge to describe many different effects and their subtle interplay at a high precision. The development of sophisticated empirical potentials for water 1-10 , allowed to gain insights into water's behavior and its thermodynamic properties [11][12][13] , such as, density maxima, heat capacity and effects of supercooling. However, empirical models lack transferability and might fail if used under conditions away from their fitting range. Most importantly, as soon as water takes an active role in a chemical process, either as a strongly interacting solvent, or for example as a source of protons, the electronic properties of the water molecule need to be taken into account. In this respect, first-principles methods offer the possibility to describe all the underlying physics on the same footing, simplifying the treatment of intra-and inter-molecular interactions. The capability to reproduce properties of complex systems such as liquid water can therefore be used to judge the sophistication and predictive power of a given quantum mechanical model. Density functional theory (DFT) is the most used quantum mechanical method employed for studying physical and chemical properties of condensed phase systems. Many DFT based simulation of bulk water have been reported in the literature, and in this context three main methods of sampling the phase space can be recognized 14 : the Car-Parrinello molecula...

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Benchmark oxygen-oxygen pair-distribution function of ambient water from x-ray diffraction measurements with a wide Q-range

Cited by 456 publications

References 46 publications

Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions

Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions

Room temperature compressibility and diffusivity of liquid water from first principles

Bulk Liquid Water at Ambient Temperature and Pressure from MP2 Theory

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