Molecular-dynamics simulation of liquid water with an<i>ab initio</i>flexible water-water interaction potential. II. The effect of internal vibrations on the time correlation functions

Mw, Evans; Refson, Keith; Kn, Swamy; Lie, G. C.; Clementi, E.

doi:10.1103/physreva.36.3935

Cited by 38 publications

(15 citation statements)

References 29 publications

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“…The first such potential, MCY, was developed by Matsuoka et al The MCY potential was parametrized by fitting two analytical functions to reproduce the energetics of 66 water dimer structures calculated at the configuration interaction level including single excitations (CIS). The original MCY potential was subsequently used as a starting point for further improvements which led to the development of a new version of the potential with flexible monomers, a refinement of the parameters based on the analysis of the vibrational frequencies, − and other more general reparameterizations . Several strictly pairwise PEFs, derived entirely from ab initio data, were proposed in the 1990s, , which served as a starting point for subsequent developments of rigorous many-body representations of the interaction energies (see section ).…”

Section: Pairwise Additive Analytical Potential Energy Functionsmentioning

confidence: 99%

Modeling Molecular Interactions in Water: From Pairwise to Many-Body Potential Energy Functions

et al. 2016

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Almost 50 years have passed from the first computer simulations of water, and a large number of molecular models have been proposed since then to elucidate the unique behavior of water across different phases. In this article, we review the recent progress in the development of analytical potential energy functions that aim at correctly representing many-body effects. Starting from the many-body expansion of the interaction energy, specific focus is on different classes of potential energy functions built upon a hierarchy of approximations and on their ability to accurately reproduce reference data obtained from state-of-the-art electronic structure calculations and experimental measurements. We show that most recent potential energy functions, which include explicit short-range representations of two-body and three-body effects along with a physically correct description of many-body effects at all distances, predict the properties of water from the gas to the condensed phase with unprecedented accuracy, thus opening the door to the long-sought “universal model” capable of describing the behavior of water under different conditions and in different environments.

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Section: Pairwise Additive Analytical Potential Energy Functionsmentioning

confidence: 99%

Modeling Molecular Interactions in Water: From Pairwise to Many-Body Potential Energy Functions

et al. 2016

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“…An ab initio representation of water across all the different phases has been an elusive goal since the early days of computer simulations. [83][84][85][86] . Although models based on correlated wavefunction theories (WFT) can, in principle, provide such a long-sought after ab initio representation of water without resorting to ad hoc approximations or empirical parameterizations, the associated computational cost precludes the application of WFT models to systems containing more than a handful of water molecules.…”

Section: Discussionmentioning

confidence: 99%

Elevating Density Functional Theory to Chemical Accuracy for Water Simulations through a Density-Corrected Many-Body Formalism

Dasgupta

Lambros

Perdew

et al. 2021

Preprint

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Kohn-Sham density functional theory (DFT) has been extensively used to model the properties of water. Albeit maintaining a good balance between accuracy and efficiency, no density functional has so far achieved the degree of accuracy necessary to correctly predict the properties of water across the entire phase diagram. The recent development of the strongly constrained and appropriately normed (SCAN) functional has renewed the interest in ab initio simulations of liquid water, yielding promising results that are, however, still unable to reproduce all the experimental data. Here, we present density-corrected SCAN (DC-SCAN) calculations for water which, minimizing density-driven errors, elevate the accuracy of the SCAN functional to that of coupled cluster theory, the “gold standard” for chemical accuracy. Building upon the accuracy and efficiency of DC-SCAN within a many-body formal- ism, we introduce a data-driven many-body potential energy function, the MB-SCAN(DC) PEF, that is able to quantitatively reproduce coupled cluster reference values for interaction, binding, and individual many-body energies of water clusters. Importantly, the properties of liquid water calculated from molecular dynamics simulations carried out with the MB- SCAN(DC) PEF are found to be in excellent agreement with the experimental data, which thus demonstrates that MB-SCAN(DC) is effectively the first DFT-based model that correctly describes water from the gas to the condensed phase. Since the many-body formalism adopted by the present MB-SCAN(DC) PEF for water is general, we believe it can open the door to the routine development of data-driven many-body PEFs for predictive simulations of generic (small) molecules in the gas, liquid, and solid phases.

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“…An ab initio representation of water across all the different phases has been an elusive goal since the early days of computer simulations. [98][99][100][101] . Although models based on correlated wavefunction theories (WFT) can, in principle, provide such a long-sought after ab initio representation of water without resorting to ad hoc approximations or empirical parameterizations, the associated computational cost precludes the application of WFT models to systems containing more than a handful of water molecules.…”

Section: Discussionmentioning

confidence: 99%

Elevating Density Functional Theory to Chemical Accuracy for Water Simulations through a Density-Corrected Many-Body Formalism

Dasgupta

Lambros

Perdew

et al. 2021

Preprint

View full text Add to dashboard Cite

Density functional theory (DFT) has been extensively used to model the properties of water. Albeit maintaining a good balance between accuracy and efficiency, no density functional has so far achieved the degree of accuracy necessary to correctly predict the properties of water across the entire phase diagram. Here, we present density-corrected SCAN (DC-SCAN) calculations for water which, minimizing density-driven errors, elevate the accuracy of the SCAN functional to that of “gold standard” coupled-cluster theory. Building upon the accuracy of DC-SCAN within a many-body formalism, we introduce a data-driven many-body potential energy function, MB-SCAN(DC), that quantitatively reproduces coupled cluster reference values for interaction, binding, and individual many-body energies of water clusters. Importantly, molecular dynamics simulations carried out with MB-SCAN(DC) also reproduce the properties of liquid water, which thus demonstrates that MB-SCAN(DC) is effectively the first DFT-based model that correctly describes water from the gas to the liquid phase.

show abstract

Molecular-dynamics simulation of liquid water with anab initioflexible water-water interaction potential. II. The effect of internal vibrations on the time correlation functions

Cited by 38 publications

References 29 publications

Modeling Molecular Interactions in Water: From Pairwise to Many-Body Potential Energy Functions

Modeling Molecular Interactions in Water: From Pairwise to Many-Body Potential Energy Functions

Elevating Density Functional Theory to Chemical Accuracy for Water Simulations through a Density-Corrected Many-Body Formalism

Elevating Density Functional Theory to Chemical Accuracy for Water Simulations through a Density-Corrected Many-Body Formalism

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