<i>Ab initio</i> molecular dynamics simulation of liquid water and water–vapor interface

Vassilev, PD Peter; Hartnig, CB Christoph; Koper, Mtm Marc; Frechard, F G; Santen, Rutger A. van

doi:10.1063/1.1413515

Cited by 73 publications

(71 citation statements)

References 39 publications

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“…A large number of workers in the field have repeated these ab initio simulations to investigate various aspects of the liquid and the methodology. [53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68] From these simulations, it becomes clear that DFT, in its various implementations, currently provides a rather reasonable but imperfect model for liquid water. For example, the hydrogen bonding pattern is sound, but the resulting liquid might be overor understructured depending on the density functional employed.…”

Section: A Introductionmentioning

confidence: 99%

Ab initio molecular dynamics using hybrid density functionals

Guidon

Schiffmann

Hutter

et al. 2008

The Journal of Chemical Physics

235

262

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Ab initio molecular dynamics simulations with hybrid density functionals have so far found little application due to their computational cost. In this work, an implementation of the Hartree-Fock exchange is presented that is specifically targeted at ab initio molecular dynamics simulations of medium sized systems. We demonstrate that our implementation, which is available as part of the CP2K/Quickstep program, is robust and efficient. Several prescreening techniques lead to a linear scaling cost for integral evaluation and storage. Integral compression techniques allow for in-core calculations on systems containing several thousand basis functions. The massively parallel implementation respects integral symmetry and scales up to hundreds of CPUs using a dynamic load balancing scheme. A time-reversible multiple time step scheme, exploiting the difference in computational efficiency between hybrid and local functionals, brings further time savings. With extensive simulations of liquid water, we demonstrate the ability to perform, for several tens of picoseconds, ab initio molecular dynamics based on hybrid functionals of systems in the condensed phase containing a few thousand Gaussian basis functions. Ab initio molecular dynamics simulations with hybrid density functionals have so far found little application due to their computational cost. In this work, an implementation of the Hartree-Fock exchange is presented that is specifically targeted at ab initio molecular dynamics simulations of medium sized systems. We demonstrate that our implementation, which is available as part of the CP2K/Quickstep program, is robust and efficient. Several prescreening techniques lead to a linear scaling cost for integral evaluation and storage. Integral compression techniques allow for in-core calculations on systems containing several thousand basis functions. The massively parallel implementation respects integral symmetry and scales up to hundreds of CPUs using a dynamic load balancing scheme. A time-reversible multiple time step scheme, exploiting the difference in computational efficiency between hybrid and local functionals, brings further time savings. With extensive simulations of liquid water, we demonstrate the ability to perform, for several tens of picoseconds, ab initio molecular dynamics based on hybrid functionals of systems in the condensed phase containing a few thousand Gaussian basis functions. Ab initio molecular dynamics using hybrid density functionals

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Section: A Introductionmentioning

confidence: 99%

Ab initio molecular dynamics using hybrid density functionals

Guidon

Schiffmann

Hutter

et al. 2008

The Journal of Chemical Physics

235

262

View full text Add to dashboard Cite

show abstract

“…[8][9][10] Quite recently another type of DFT-based molecular dynamics ͑MD͒ simulations, which differs from the CP method in the treatment of the electronic degrees of freedom, was also successfully applied to study bulk liquid water and the water-vapor interface. 11 The results of these so-called first-principles molecular dynamics simulations of liquid water were very promising and an increasing number of groups is now applying the same techniques to study water-metal interfaces in relation, for example, to heterogeneous reactions at transition metal surfaces, ͑electro͒chemi-cal processes, and the process of electron transfer through the interface. [12][13][14][15][16][17][18][19][20][21][22] Historically, one of the first and most successful theoretical models for electron transfer processes was proposed by Marcus in the second half of the 1950s.…”

Section: Introductionmentioning

confidence: 99%

Ab initio studies of a water layer at transition metal surfaces

Vassilev

Santen

Koper

2005

The Journal of Chemical Physics

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This paper presents a detailed study of a water adlayer adsorbed on Pt(111) and Rh(111) surfaces using periodic density functional theory methods. The interaction between the metal surface and the water molecules is assessed from molecular dynamics simulation data and single point electronic structure calculations of selected configurations. It is argued that the electron bands around the Fermi level of the metal substrate extend over the water adlayer. As a consequence in the presence of the water layer the surface as a whole still maintains its metallic conductivity—a result of a crucial importance for understanding the process of electron transfer through the water/metal interface and electrochemical reactions in particular. Our results also indicate that there exists a weak bond between the hydrogen of the water and the Rh metal atoms as opposed to the widespread (classical) models based on purely repulsive interaction. This suggests that the commonly used classical interactions potentials adopted for large scale molecular dynamics simulations of water/metal interfaces may need revision. Two adsorption models of water on transition metals with the OH bonds pointing towards or away of the surface are also examined. It is shown that due to the very close values of their adsorption energies one should consider the real structure of water on the surface as a mixture of these simple “up” and “down” models. A model for the structure of the adsorbed water layer on Rh(111) is proposed in terms of statistical averages from molecular dynamics simulations.

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“…This means that the London dispersion or van der Waals (vdW) interaction is not properly accounted for in these studies. Still, in particular, the PBE-GGA functional [13] is able to reproduce water properties reasonably well [5,[14][15][16] because PBE gives a reliable description of the hydrogenbonding which is obviously crucial for a proper treatment of water.However, several studies have already shown that dispersive forces contribute significantly to the stability of water on metal surfaces. [17][18][19][20] Feibelman pointed at the important role of vdW forces in water structures at metallic surfaces.…”

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confidence: 99%

Dispersive interactions in water bilayers at metallic surfaces: A comparison of the PBE and RPBE functional including semiempirical dispersion corrections

2012

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The accuracy and reliability of the density functional theory (DFT)-D approach to account for dispersion effects in first-principles studies of water-metal interfaces has been addressed by studying several water-metal systems. In addition to performing periodic DFT calculations for semi-infinite substrates using the popular PBE and RPBE functionals, the water dimer and water-metal atom systems have also been treated by coupled-cluster calculations. We show that indeed semiempirical dispersion correction schemes can be used to yield thermodynamically stable water bilayers at surfaces. However, the actual density functional needs to be chosen carefully. Whereas the dispersion-corrected RPBE functional yields a good description of both the water-water and the water-metal interaction, the dispersion-corrected PBE functional overestimates the energies of both systems. In contrast thereto, the adsorption distances predicted by the PBE functional is hardly changed due to the additional dispersion interaction, explaining the good performance of previous DFT-PBE studies of water-metal systems.

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Ab initio molecular dynamics simulation of liquid water and water–vapor interface

Cited by 73 publications

References 39 publications

Ab initio molecular dynamics using hybrid density functionals

Ab initio molecular dynamics using hybrid density functionals

Ab initio studies of a water layer at transition metal surfaces

Dispersive interactions in water bilayers at metallic surfaces: A comparison of the PBE and RPBE functional including semiempirical dispersion corrections

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