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

Miceli, Giacomo; Gironcoli, Stefano de; Pasquarello, Alfredo

doi:10.1063/1.4905333

Cited by 74 publications

(140 citation statements)

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“…These results are in agreement with previous NVT simulations, 42 and a recent NPT simulation performed with the rVV10 functional in Ref. 74, where a reparameterization of the functional was proposed to cure this deficiency. Even though at the limit of statistical accuracy, both the inclusion of the D3 correction and the use of hybrid functionals reduce the height of the first peak of the g OO (r) for PBE, while the ADMM approximation influences the equilibrium density by ∼2% and leads to slightly more TABLE I.…”

Section: Structural Propertiessupporting

confidence: 82%

“…The introduction of dispersion forces, either in a semi-empirical way, such as the Grimme's D3 correction, or by including an explicit non-local term in the functional, such as in the van der Waals density functionals, 69,70 improves the liquid description, but in general gives too dense water (5%-10%). 38,40,42,74,135,136 An illustration of the change induced by van der Waals interactions is provided in Figure 2(a), where BLYP and PBE0-D3 RDF's are shown. In particular, the distributions of the 4th and 5th neighboring waters show a clear separation between the first and second coordination shells in the BLYP case, whereas these peaks move closer at the PBE0-D3.…”

Section: Structural Propertiesmentioning

confidence: 99%

“…[69][70][71][72] The performance of both these approaches has been extensively tested and the results show a systematic improvement upon the uncorrected GGA or hybrid functionals. 30,34,40,42,51,73,74 In this work, we assess the performance of various methods, with a focus on functionals from the 5th rung. In particular, the structural and dynamical properties of bulk liquid water have been studied by means of Monte Carlo (MC) and MD simulations.…”

Section: Introductionmentioning

confidence: 99%

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Probing the structural and dynamical properties of liquid water with models including non-local electron correlation

Ben

Hutter

VandeVondele

2015

The Journal of Chemical Physics

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Water is a ubiquitous liquid that displays a wide range of anomalous properties and has a delicate structure that challenges experiment and simulation alike. The various intermolecular interactions that play an important role, such as repulsion, polarization, hydrogen bonding, and van der Waals interactions, are often difficult to reproduce faithfully in atomistic models. Here, electronic structure theories including all these interactions at equal footing, which requires the inclusion of non-local electron correlation, are used to describe structure and dynamics of bulk liquid water. Isobaric-isothermal (NpT) ensemble simulations based on the Random Phase Approximation (RPA) yield excellent density (0.994 g/ml) and fair radial distribution functions, while various other density functional approximations produce scattered results (0.8-1.2 g/ml). Molecular dynamics simulation in the microcanonical (NVE) ensemble based on Møller-Plesset perturbation theory (MP2) yields dynamical properties in the condensed phase, namely, the infrared spectrum and diffusion constant. At the MP2 and RPA levels of theory, ice is correctly predicted to float on water, resolving one of the anomalies as resulting from a delicate balance between van der Waals and hydrogen bonding interactions. For several properties, obtaining quantitative agreement with experiment requires correction for nuclear quantum effects (NQEs), highlighting their importance, for structure, dynamics, and electronic properties. A computed NQE shift of 0.6 eV for the band gap and absorption spectrum illustrates the latter. Giving access to both structure and dynamics of condensed phase systems, non-local electron correlation will increasingly be used to study systems where weak interactions are of paramount importance. Water is a ubiquitous liquid that displays a wide range of anomalous properties and has a delicate structure that challenges experiment and simulation alike. The various intermolecular interactions that play an important role, such as repulsion, polarization, hydrogen bonding, and van der Waals interactions, are often difficult to reproduce faithfully in atomistic models. Here, electronic structure theories including all these interactions at equal footing, which requires the inclusion of non-local electron correlation, are used to describe structure and dynamics of bulk liquid water. Isobaricisothermal (NpT) ensemble simulations based on the Random Phase Approximation (RPA) yield excellent density (0.994 g/ml) and fair radial distribution functions, while various other density functional approximations produce scattered results (0.8-1.2 g/ml). Molecular dynamics simulation in the microcanonical (NVE) ensemble based on Møller-Plesset perturbation theory (MP2) yields dynamical properties in the condensed phase, namely, the infrared spectrum and diffusion constant. At the MP2 and RPA levels of theory, ice is correctly predicted to float on water, resolving one of the anomalies as resulting from a delicate balance between van der Waals and hyd...

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Section: Structural Propertiessupporting

confidence: 82%

Section: Structural Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Probing the structural and dynamical properties of liquid water with models including non-local electron correlation

Ben

Hutter

VandeVondele

2015

The Journal of Chemical Physics

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“…Björkman et al further proposed b ¼ 9.15 for VV10 by fitting to the binding energies of 26 layered materials [18], and we obtained the same number for rVV10. Reference [39] found b ¼ 9.3 for the structural properties of water. These results highlight the flexibility of the VV10 and rVV10 methods but also point out the need for a new approach with a single set of vdW empirical parameters for all materials.…”

Section: Theory: Parameters In Scanþrvv10mentioning

confidence: 99%

Versatile van der Waals Density Functional Based on a Meta-Generalized Gradient Approximation

et al. 2016

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A "best-of-both-worlds" van der Waals (vdW) density functional is constructed, seamlessly supplementing the strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation for short-and intermediate-range interactions with the long-range vdW interaction from rVV10, the revised Vydrov-van Voorhis nonlocal correlation functional. The resultant SCANþrVV10 is the only vdW density functional to date that yields excellent interlayer binding energies and spacings, as well as intralayer lattice constants in 28 layered materials. Its versatility for various kinds of bonding is further demonstrated by its good performance for 22 interactions between molecules; the cohesive energies and lattice constants of 50 solids; the adsorption energy and distance of a benzene molecule on coinage-metal surfaces; the binding energy curves for graphene on Cu(111), Ni(111), and Co (0001) surfaces; and the rare-gas solids. We argue that a good semilocal approximation should (as SCAN does) capture the intermediate-range vdW through its exchange term. We have found an effective range of the vdW interaction between 8 and 16 Å for systems considered here, suggesting that this interaction is negligibly small at the larger distances where it reaches its asymptotic power-law decay.

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“…Norm-conserving pseudopotentials with a plane-wave cutoff of 85 Ry are used in the DFT calculations. To account for the nonlocal van der Waals dispersion, which is critical for the hydrogen-bond network [50,51,[60][61][62][63], the revised Vydrov and Van Voorhis (rVV10) van der Waals density functional [52,53] is used in the MD simulations. The short-range behavior is controlled by an empirical parameter b in the rVV10 density functional [52,53].…”

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confidence: 99%

Ab initio Electronic Structure of Liquid Water

et al. 2016

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Self-consistent GW calculations with efficient vertex corrections are employed to determine the electronic structure of liquid water. Nuclear quantum effects are taken into account through ab initio pathintegral molecular dynamics simulations. We reveal a sizable band-gap renormalization of up to 0.7 eV due to hydrogen-bond quantum fluctuations. Our calculations lead to a band gap of 8.9 eV, in accord with the experimental estimate. We further resolve the ambiguities in the band-edge positions of liquid water. The valence-band maximum and the conduction-band minimum are found at −9.4 and −0.5 eV with respect to the vacuum level, respectively. DOI: 10.1103/PhysRevLett.117.186401 Liquid water is such a ubiquitous substance that it has been the subject of upsurging research efforts for the past 30 years. Of particular importance is the electronic structure of liquid water, the significance of which has been recently highlighted in clean-energy technologies through semiconductor-assisted artificial photosynthesis [1,2]. A good understanding of the electronic structure of water is a prerequisite toward the design of photocatalytic systems with high catalytic activity.The extended hydrogen-bond network of liquid water gives rise to the formation of electronic bands. The valence band maximum (VBM) is characterized by the localized 2p z electrons of O atoms. The conduction band minimum (CBM) derives from the antibonding orbitals of O-H bonds, and is at variance much more extended. Experimentally determined positions of these band edge states have yet to reach a consensus. Early ultraviolet (UV) photoemission experiments by Delahay and collaborators reported photoemission threshold energies of 9.3 [3] and 10.06 eV [4]. More recent work by Winter et al. employed the liquid microjet technique and found a threshold energy of 9.9 eV [5]. For the unoccupied states, inverse photoemission and photoionization measurements placed the CBM at −1.2 eV with respect to the vacuum level [6,7]. This value was later revised to −0.74 eV, in light of the observation that excess electrons in liquid water could be initially captured in a localized trap state below the actual CBM [8]. Altogether, these measurements allude to a band gap of 8.7 eV, but associated with a sizable uncertainty of AE0.6 eV.To shed light on the electronic structure of water, it is necessary to resort to a fully ab initio method, which avoids the use of experimental input. Ab initio molecular dynamics (MD) simulations based on Kohn-Sham density-functional theory (DFT) have been extensively carried out to understand the structural and dynamical properties of water and of aqueous solutions. It is well recognized that the use of semilocal density functionals precludes a faithful description of the electronic structure and the predicted band gap of liquid water is apparently too small [9,10]. Hybrid functionals improve the description of the electronic structure [10], but the mixing parameter of the Fock exchange is not known a priori without the input from experiment ...

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

Cited by 74 publications

References 64 publications

Probing the structural and dynamical properties of liquid water with models including non-local electron correlation

Probing the structural and dynamical properties of liquid water with models including non-local electron correlation

Versatile van der Waals Density Functional Based on a Meta-Generalized Gradient Approximation

Ab initio Electronic Structure of Liquid Water

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