Low-order many-body interactions determine the local structure of liquid water

Riera, Marc; Lambros, Eleftherios; Nguyen, Thanh; Götz, Andreas W.; Paesani, Francesco

doi:10.1039/c9sc03291f

Cited by 48 publications

(81 citation statements)

References 55 publications

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“…MB-pol [54][55][56] and MB-DFT 43 are explicit many-body models derived from the many-body expansion (MBE) of the energy, which represents the energy of a system of N "bodies" (i.e., distinct atoms or molecules) as the sum of all the individual n-body contributions, with n ≤ N. 57 The MBE is formally expressed as…”

Section: Explicit Many-body Models: Mb-pol and Mb-dftmentioning

confidence: 99%

Assessing the Accuracy of the SCAN Functional for Water through a Many-Body Analysis of the Adiabatic Connection Formula

Lambros

Paesani

2021

J. Chem. Theory Comput.

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We present a systematic analysis of the accuracy of a series of SCANα functionals for water, with varying fractions (α) of exact exchange, which are constructed through the adiabatic connection formula. Our results indicate that that all SCANα functionals exhibit substantial errors in the representation of the water 2-body energies. Importantly, the inclusion of exact exchange is found to have opposite effects on the ability of the SCANα functionals to describe the interaction energies of water clusters with 2-dimensional and 3-dimensional hydrogen-bonding arrangements. These errors are found to directly affect the ability of the SCANα functionals to describe the structure of liquid water at ambient conditions, which is investigated using explicit many-body models (MB-SCANα) derived from the corresponding SCANα data. In particular, it is found that all MB-SCANα models predict a more compact first hydration shell, which results in a denser liquid with a more ice-like structure. These ap-parent opposite trends can be explained by the inability of all SCANα functionals to provide a balanced description of the water 2B and 3B energies at the fundamental level. The analyses presented in this study provide new insights that can guide future developments of improved exchange-correlation functionals for water. File list (2) download file view on ChemRxiv manuscript.pdf (2.26 MiB) download file view on ChemRxiv supporting_info.pdf (265.59 KiB)

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Section: Explicit Many-body Models: Mb-pol and Mb-dftmentioning

confidence: 99%

Assessing the Accuracy of the SCAN Functional for Water through a Many-Body Analysis of the Adiabatic Connection Formula

Lambros

Paesani

2021

J. Chem. Theory Comput.

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“…Overall, methodology has made a key progress and will continue in this direction for all types of polarizable force fields as the accessible computer power quickly increases reducing therefore the computational gap with additive potentials. Whereas specialized highly accurate water potentials based on many-body expansions emerge such as MBPOL (Riera et al, 2019) and allow for a better understanding of fine physical effects in clusters and bulk water, the availability of general polarizable force fields such as AMOEBA offering water (Ren and Ponder, 2003), ions, organochlorine compounds (Mu et al, 2014), proteins and nucleic acids (Shi et al, 2013; Zhang et al, 2018) now enables performing enough sampling to achieve highly accurate and biologically meaningful simulations. The Drude approaches parametrization is expanding as well (Lamoureux et al, 2003; Chowdhary et al, 2013a,b; Lopes et al, 2013).…”

Section: Are Polarizable Simulations Computationally Tractable?mentioning

confidence: 99%

Accurate Biomolecular Simulations Account for Electronic Polarization

Melcr

Piquemal

2019

Front. Mol. Biosci.

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In this perspective, we discuss where and how accounting for electronic many-body polarization affects the accuracy of classical molecular dynamics simulations of biomolecules.While the effects of electronic polarization are highly pronounced for molecules with an opposite total charge, they are also non-negligible for interactions with overall neutral molecules. For instance, neglecting these effects in important biomolecules like amino acids and phospholipids

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“…The MB-DFT PEFs generalize the MBE formalism adopted to develop the MB-pol PEF of water by replacing the 2-body (2B) and 3-body (3B) terms, which were originally calculated at the CCSD(T)/CBS level of theory, with corresponding terms calculated using an arbitrary density functional. 53 It has been shown that the MB-DFT PEFs closely reproduce the structural properties of liquid water calculated from fully ab initio MD simulations carried out with the same density functional. 53 The MB-DFT family of hybrid data-driven/physics-based PEFs is particularly appealing for quantum mechanics/molecular mechanics (QM/MM) simulations of systems that are either too computationally expensive to be treated at a fully quantum-mechanical (QM) level or cannot be described using molecular mechanics (MM) models since they involve rearrangements of chemical bonds.…”

Section: Introductionmentioning

confidence: 78%

“…53 It has been shown that the MB-DFT PEFs closely reproduce the structural properties of liquid water calculated from fully ab initio MD simulations carried out with the same density functional. 53 The MB-DFT family of hybrid data-driven/physics-based PEFs is particularly appealing for quantum mechanics/molecular mechanics (QM/MM) simulations of systems that are either too computationally expensive to be treated at a fully quantum-mechanical (QM) level or cannot be described using molecular mechanics (MM) models since they involve rearrangements of chemical bonds. Likewise, while ML approaches can, by construction, model bond rearrangements, their behavior is highly dependent on the composition the datasets and level of theory used in the training process.…”

Section: Introductionmentioning

confidence: 78%

General Many-Body Framework for Data-Driven Potentials with Arbitrary Quantum Mechanical Accuracy: Water as a Case Study

Lambros¹,

Dasgupta²,

Palos³

et al. 2021

Preprint

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<div> <div> <div> <p> </p><div> <div> <div> <p>We present a general framework for the development of data-driven many-body (MB) potential energy functions (MB-QM PEFs) that represent the interactions between small molecules at an arbitrary quantum-mechanical (QM) level of theory. As a demonstration, a family of MB-QM PEFs for water are rigorously derived from density functionals belonging to differ- ent rungs across Jacob’s ladder of approximations within density functional theory (MB-DFT) as well as from Møller-Plesset perturbation theory (MB-MP2). Through a systematic analysis of individual many-body contributions to the interaction energies of water clusters, we demonstrate that all MB-QM PEFs preserve the same accuracy as the corresponding ab initio calculations, with the exception of those derived from density functionals within the generalized gradient approximation (GGA). The differences between the DFT and MB-DFT results are traced back to density-driven errors that prevent GGA functionals from accurately representing the underlying molecular interactions for different cluster sizes and hydrogen-bonding arrangements. We show that this shortcoming may be overcome, within the many-body formalism, by using density-corrected functionals that provide a more consistent representation of each individual many-body contribution. This is demonstrated through the development of a MB-DFT PEF derived from density-corrected PBE-D3 data, which more accurately reproduce the corresponding ab initio results. </p> </div> </div> </div> </div> </div> </div>

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Low-order many-body interactions determine the local structure of liquid water

Abstract: Two-body and three-body energies, modulated by higher-body terms and nuclear quantum effects, determine the structure of liquid water and require sub-chemical accuracy that is achieved by the MB-pol model but not by existing DFT functionals.

Cited by 48 publications

References 55 publications

Assessing the Accuracy of the SCAN Functional for Water through a Many-Body Analysis of the Adiabatic Connection Formula

Assessing the Accuracy of the SCAN Functional for Water through a Many-Body Analysis of the Adiabatic Connection Formula

Accurate Biomolecular Simulations Account for Electronic Polarization

General Many-Body Framework for Data-Driven Potentials with Arbitrary Quantum Mechanical Accuracy: Water as a Case Study

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