The random phase approximation applied to ice

Macher, Markus; Klimeš, Jiří; Franchini, Cesare; Kresse, Georg

doi:10.1063/1.4865748

Cited by 51 publications

(62 citation statements)

References 103 publications

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“…The equilibrium parameters calculated at the MP2, PWPB95-D3, and RPA, obtained from the lattice parameter optimization curves of Figure 5, are reported in Table II. At the RPA level, the computed equilibrium molecular volume and cohesive energy compare well with 32.8 Å 3 and −52.5 kJ/mol calculated by Macher et al 159 as well as at the MP2 level the E coh is in good agreement with the value of −58.7 kJ/mol reported by Gillan and coworkers. 160 The results obtained at the PBE level reproduce various previous calculations 74,159,161,162 (see also 164,165 Compared to experiment, RPA underestimates the result, but as already pointed out in Ref.…”

Section: Density Of Ice Ihsupporting

confidence: 88%

“…160 The results obtained at the PBE level reproduce various previous calculations 74,159,161,162 (see also 164,165 Compared to experiment, RPA underestimates the result, but as already pointed out in Ref. 159, this depends on the starting orbitals used. While PBE orbitals lead to underbinding, HF orbitals lead to overbinding, and hybrids can be tuned to yield the correct results.…”

Section: Density Of Ice Ihsupporting

confidence: 82%

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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

102

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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: Density Of Ice Ihsupporting

confidence: 88%

Section: Density Of Ice Ihsupporting

confidence: 82%

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

102

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“…The calculated results are compared with recent theoretical studies. 11,33,34,38,47,63,67 The O-H bond-length in the H 2 O monomer is 0.973 Å, close to the experimental values within 0.02 Å. 64 There are many theoretical studies using various functionals, including the 'hybrid' B3LYP method which adopted an all-electron 6311G(p,d) basis set, 11,12 X3LYP which contains van der Waals interactions, 35,35 and the ab initio Hartree-Fock method within coupled-cluster singles, doubles, triples (HF-CCSDT) wave function.…”

Section: Iiia Structures Of the H 2 O Molecule The H 2 O Dimer Anmentioning

confidence: 99%

The accurate calculation of the band gap of liquid water by means of GW corrections applied to plane-wave density functional theory molecular dynamics simulations

Fang

Koster

et al. 2015

Phys. Chem. Chem. Phys.

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Knowledge about the intrinsic electronic properties of water is imperative for understanding the behaviour of aqueous solutions that are used throughout biology, chemistry, physics, and industry. The calculation of the electronic band gap of liquids is challenging, because the most accurate ab initio approaches can be applied only to small numbers of atoms, while large numbers of atoms are required for having configurations that are representative of a liquid. Here we show that a high-accuracy value for the electronic band gap of water can be obtained by combining beyond-DFT methods and statistical time-averaging. Liquid water is simulated at 300 K using a plane-wave density functional theory molecular dynamics (PW-DFT-MD) simulation and a van der Waals density functional (optB88-vdW).After applying a self-consistent GW correction the band gap of liquid water at 300 K is calculated as 7.3 eV, in good agreement with recent experimental observations in the literature (6.9 eV). For simulations of phase transformations and chemical reactions in water or aqueous solutions whereby an accurate description of the electronic structure is required, we suggest to use these advanced GW corrections in combination with the statistical analysis of quantum mechanical MD simulations.

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“…The correct descriptions of ice properties depend on accurate calculations of H-bond interactions, which however pose a challenge for DFT methods. Recently, several benchmark DFT studies have been carried out on various phases of ice, and different kinds of DFT methods have been employed in previous studies on ice, [49][50][51][79][80][81][82][83][84] but no one functional has been commonly the preferred choice in the studies of ice. Thus, we evaluated the performance of 16 different DFT methods on ice Ih, VIII, IX, and XI.…”

mentioning

confidence: 99%

Raman and IR Spectra of Ice Ih and Ice XI with an Assessment of DFT Methods

Liu

Ojamäe

2016

J. Phys. Chem. B

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IR and Raman spectroscopic technology can be directly used to identify the occurrence of ferroelectric ice XI in laboratory or extraterrestrial settings. The performance of 16 different DFT methods applied on the ice Ih, VIII, IX, and XI crystal phases is evaluated. Based on a selected DFT computational scheme, the IR and Raman spectra of ice Ih and XI are derived and compared. When the spectra, both IR and Raman, of ice Ih and ice XI are compared, the librational vibrations are found to be the most affected by the proton ordering. The spectroscopic fingerprint of ice XI can be used to distinguish ferroelectric ice XI from ice Ih in the universe. Furthermore, the existence of only one kind of H-bond in ice Ih is demonstrated from the overlapping subspectra for different types of H-bonded pair configurations in 16 isomers of ice Ih, which provides an illustration to the historic debate on whether one or two kinds of H-bonds existed in ice.

Funding agencies: Swedish Research Council (VR); Swedish Supercomputer Center (SNIC/NSC); State Scholarship Fund of China Scholarship Council [201206060016]

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The random phase approximation applied to ice

Cited by 51 publications

References 103 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

The accurate calculation of the band gap of liquid water by means of GW corrections applied to plane-wave density functional theory molecular dynamics simulations

Raman and IR Spectra of Ice Ih and Ice XI with an Assessment of DFT Methods

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