On the accuracy of van der Waals inclusive density-functional theory exchange-correlation functionals for ice at ambient and high pressures

Santra, Biswajit; Klimeš, Jiří; Tkatchenko, Alexandre; Alfè, Dario; Slater, Ben; Michaelides, Angelos; Car, Roberto; Scheffler, Matthias

doi:10.1063/1.4824481

Cited by 130 publications

(208 citation statements)

References 134 publications

(215 reference statements)

Supporting

Mentioning

185

Contrasting

Order By: Relevance

“…Results are shown in order of increasing density for both 2D and 3D ice. On comparing 2D and 3D ice we find that while vdW is important in 2D it plays a smaller role than it is known to play in 3D [11,25]. This can be seen, for example, by comparing the slopes of the PBE curves in 2D and 3D, where it can be seen that the PBE curve in 3D is much steeper.…”

Section: Fig 4 Binding Energy Difference E − Ementioning

confidence: 72%

“…Of the various methods available, diffusion Monte Carlo (DMC) is particularly attractive [18][19][20][21][22][23][24]. First, DMC has already been shown to offer the requisite accuracy for bulk ice phases by producing results in excellent agreement with experiment [11,12,25,26]. Second, owing to recent improvements in computational efficiency [27], it is now possible to obtain converged results on the large unit cells that must be considered when treating 2D ice with a many-body electronic structure approach.…”

Section: Published By the American Physical Society Under The Terms Omentioning

confidence: 99%

See 1 more Smart Citation

Evidence for stable square ice from quantum Monte Carlo

et al. 2016

Self Cite

View full text Add to dashboard Cite

Recent experiments on ice formed by water under nanoconfinement provide evidence for a two-dimensional (2D) "square ice" phase. However, the interpretation of the experiments has been questioned and the stability of square ice has become a matter of debate. Partially this is because the simulation approaches employed so far (force fields and density functional theory) struggle to accurately describe the very small energy differences between the relevant phases. Here we report a study of 2D ice using an accurate wave-function based electronic structure approach, namely diffusion Monte Carlo (DMC). We find that at relatively high pressure, square ice is indeed the lowest enthalpy phase examined, supporting the initial experimental claim. Moreover, at lower pressures, a "pentagonal ice" phase (not yet observed experimentally) has the lowest enthalpy, and at ambient pressure, the "pentagonal ice" phase is degenerate with a "hexagonal ice" phase. Our DMC results also allow us to evaluate the accuracy of various density functional theory exchange-correlation functionals and force field models, and in doing so we extend the understanding of how such methodologies perform to challenging 2D structures presenting dangling hydrogen bonds. DOI: 10.1103/PhysRevB.94.220102 Recent transmission electron microscopy (TEM) measurements and classical molecular dynamics simulations report that a new two-dimensional (2D) square phase of ice forms [1]. This phase is not part of the bulk ice phase diagram, but it was suggested that it is stabilized under confinement because of lateral pressure, estimated to be in the gigapascal (GPa), arising from the van der Waals (vdW) attraction between the graphene sheets. However, these experiments have been questioned [2], with it even being suggested that it is sodium chloride contamination and not ice that is responsible for the square symmetry observed. So far, it is not clear under what conditions (if any) square ice is stable.Theoretical investigations of the stability of confined 2D ice at high lateral pressures can, in principle, help in disentangling this issue and in complementing experimental findings [3][4][5][6][7][8][9][10]. From a theoretical perspective, the prediction of square 2D ice can be traced back to Nagle's 1970's "unit model" of ice [3]. However, later atomistic force field (FF) simulations found that 2D ice prefers a buckled rhombic structure [4,5]. More recently, density functional theory (DFT) based investigations [6-9] have been performed. However, these have produced qualitatively different results depending on the precise details of the calculations and, in particular, on the choice of exchange-correlation (XC) functional. For instance, Chen et al. [7] found hexagonal and pentagonal structures to be stable phases at low pressures (Fig. 1). They also found that square ice is only stable in the GPa pressure * angelos.michaelides@ucl.ac.uk Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further...

show abstract

Section: Fig 4 Binding Energy Difference E − Ementioning

confidence: 72%

Section: Published By the American Physical Society Under The Terms Omentioning

confidence: 99%

Evidence for stable square ice from quantum Monte Carlo

et al. 2016

Self Cite

View full text Add to dashboard Cite

show abstract

“…41 This model of ice has been adopted in several theoretical studies to test the accuracy of density functionals in describing solid water networks. [42][43][44] Figure 2 shows a top-view perspective along the c axis of the ordered Bernal-Fowler model of ice. The unit cell contains 12 water molecules and belongs to the P6 3 cm(C 3 6v ) space group.…”

Section: I H Phase Of Icementioning

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

View full text Add to dashboard Cite

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.

show abstract

“…For example, water has several distinct ice polymorphs that have lattice energies within 35 meV/H 2 O of each other. [1][2][3][4][5][6] Likewise for water clusters, most notably the water hexamer, there are several isomers that have energies within just 5 meV/H 2 O. 5,7,8 Furthermore, in biological applications there can be numerous shallow energy minima with different conformations.…”

Section: Introductionmentioning

confidence: 99%

Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

Al-Hamdani

Alfè

Lilienfeld

et al. 2014

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we show that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B3N3H6) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.

show abstract

On the accuracy of van der Waals inclusive density-functional theory exchange-correlation functionals for ice at ambient and high pressures

Cited by 130 publications

References 134 publications

Evidence for stable square ice from quantum Monte Carlo

Evidence for stable square ice from quantum Monte Carlo

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

Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

Contact Info

Product

Resources

About