Nuclear quantum effects in liquid water from path-integral simulations using an<i>ab initio</i>force-matching approach

Spura, Thomas; John, C. Jesintha; Habershon, Scott; Kühne, Thomas D.

doi:10.1080/00268976.2014.981231

Cited by 35 publications

(53 citation statements)

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“…As can be seen in Table S2, the AI‐PIMD simulations showed that both intermolecular distances are increased due to NQE (up to 4 % for the H D …O A distance), which is consistent with previous PIMD simulations and experimental measurements of liquid water . Interestingly, however, the intramolecular O−H bonds are, on the one hand, shortened by up to 5 % (O D −HR) by NQE, whereas in bulk water they are slightly elongated .…”

Section: Resultssupporting

confidence: 89%

“…The vertical dashed lines in Figure 1 indicate the bond lengths in H 2 O (0.972 Å and 0.985 Å in the gas [6] and liquid [37] As can be seen in Table S2, the AI-PIMD simulations showed that both intermolecular distances are increased due to NQE (up to 4 % for the H D …O A distance), which is consistent with previous PIMD simulations and experimental measurements of liquid water. [7,33] Interestingly, however, the intramolecular OÀ H bonds are, on the one hand, shortened by up to 5 % (O D À HR) by NQE, whereas in bulk water they are slightly elongated. [33] Moreover, the intramolecular angles are increased by as much as 1 % (H R À O D À H D ), which again contrasts with the bulk, where the intramolecular angles are slightly decreased due to NQE.…”

Section: Methodsmentioning

confidence: 99%

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Opposing Electronic and Nuclear Quantum Effects on Hydrogen Bonds in H₂O and D₂O

2019

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The effect of extending the OÀ H bond length(s) in water on the hydrogen-bonding strength has been investigated using static ab initio molecular orbital calculations. The "polar flattening" effect that causes a slight σ-hole to form on hydrogen atoms is strengthened when the bond is stretched, so that the σ-hole becomes more positive and hydrogen bonding stronger. In opposition to this electronic effect, path-integral ab initio molecular-dynamics simulations show that the nuclear quantum effect weakens the hydrogen bond in the water dimer. Thus, static electronic effects strengthen the hydrogen bond in H 2 O relative to D 2 O, whereas nuclear quantum effects weaken it. These quantum fluctuations are stronger for the water dimer than in bulk water.

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Section: Resultssupporting

confidence: 89%

Section: Methodsmentioning

confidence: 99%

Opposing Electronic and Nuclear Quantum Effects on Hydrogen Bonds in H₂O and D₂O

2019

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“…This is somehow surprising, especially when considering that the type of XC functionals has a sizable impact on the peak height of the oxygen-oxygen radial distribution, as does the type of van der Waals correction. 76,77 This implies that the long-range interactions critically affects the calculation of the surface tension.…”

Section: Size Effects Of Surface Tension Simulated With Spc/fw Water mentioning

confidence: 99%

Surface tension of ab initio liquid water at the water-air interface

Nagata

Ohto

Bonn

et al. 2016

The Journal of Chemical Physics

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ABSTRACT:We report calculations of the surface tension of the water-air interface using ab initio molecular dynamics (AIMD) simulations. We investigate the simulation cell size dependence of the surface tension of water from force field molecular dynamics (MD) simulations, which show that the calculated surface tension increases with increasing simulation cell size, thereby illustrating that a correction for finite size effects is required for the small system used in the AIMD simulation. 2The AIMD simulations reveal that the double-ξ basis set overestimates the experimentally measured surface tension due to the Pulay stress, while the triple and quadruple-ξ basis sets give similar results. We further demonstrate that the van der Waals corrections critically affect the surface tension. AIMD simulations without the van der Waals correction substantially underestimate the surface tension, while van der Waals correction with the Grimme's D2 technique results in the value for the surface tension that is too high. The Grimme's D3 van der Waals correction provides a surface tension close to the experimental value. Whereas the specific choices for the van der Waals correction and basis sets critically affect the calculated surface tension, the surface tension is remarkably insensitive to the details of the exchange and correlation functionals, which highlights the impact of long-range interactions on the surface tension. These simulated values provide important benchmarks, both for improving van der Waals corrections, and AIMD simulations of aqueous interfaces.

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“…Contrarily to the previous approaches, the path integral method allows for a quantum formulation which includes, in addition to the electronic degrees of freedom, their nuclear counterpart. Such a formulation is essential for systems containing light nuclei [37,38].…”

Section: Path Integral Molecular Dynamics: Toward a Quantum Formulatimentioning

confidence: 99%

Computational Methods for Ab Initio Molecular Dynamics

Paquet

Viktor

2018

Advances in Chemistry

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Ab initio molecular dynamics is an irreplaceable technique for the realistic simulation of complex molecular systems and processes from first principles. This paper proposes a comprehensive and self-contained review of ab initio molecular dynamics from a computational perspective and from first principles. Quantum mechanics is presented from a molecular dynamics perspective. Various approximations and formulations are proposed, including the Ehrenfest, Born-Oppenheimer, and Hartree-Fock molecular dynamics. Subsequently, the Kohn-Sham formulation of molecular dynamics is introduced as well as the afferent concept of density functional. As a result, Car-Parrinello molecular dynamics is discussed, together with its extension to isothermal and isobaric processes. Car-Parrinello molecular dynamics is then reformulated in terms of path integrals. Finally, some implementation issues are analysed, namely, the pseudopotential, the orbital functional basis, and hybrid molecular dynamics.

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Nuclear quantum effects in liquid water from path-integral simulations using anab initioforce-matching approach

Cited by 35 publications

References 152 publications

Opposing Electronic and Nuclear Quantum Effects on Hydrogen Bonds in H₂O and D₂O

Opposing Electronic and Nuclear Quantum Effects on Hydrogen Bonds in H₂O and D₂O

Surface tension of ab initio liquid water at the water-air interface

Computational Methods for Ab Initio Molecular Dynamics

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Nuclear quantum effects in liquid water from path-integral simulations using anab initioforce-matching approach

Cited by 35 publications

References 152 publications

Opposing Electronic and Nuclear Quantum Effects on Hydrogen Bonds in H2O and D2O

Opposing Electronic and Nuclear Quantum Effects on Hydrogen Bonds in H2O and D2O

Surface tension of ab initio liquid water at the water-air interface

Computational Methods for Ab Initio Molecular Dynamics

Contact Info

Product

Resources

About

Opposing Electronic and Nuclear Quantum Effects on Hydrogen Bonds in H₂O and D₂O

Opposing Electronic and Nuclear Quantum Effects on Hydrogen Bonds in H₂O and D₂O