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

Despite its apparent simplicity, water displays unique behavior across the phase diagram which is strictly related to the ability of the water molecules to form dense, yet dynamic, hydrogen-bond networks that continually fluctuate in time and space. The competition between different local hydrogen-b...

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Published inChemical science (Cambridge) Vol. 1; no. 35; pp. 8211 - 8218
Main Authors Riera, Marc, Lambros, Eleftherios, Nguyen, Thuong T, Götz, Andreas W, Paesani, Francesco
Format Journal Article
LanguageEnglish
Published England Royal Society of Chemistry 21.09.2019
Subjects
Chemistry
Computer simulation
Distribution functions
Hydrogen bonding
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Many body interactions
Organic chemistry
Phase diagrams
Radial distribution
Water
Water chemistry
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Summary:Despite its apparent simplicity, water displays unique behavior across the phase diagram which is strictly related to the ability of the water molecules to form dense, yet dynamic, hydrogen-bond networks that continually fluctuate in time and space. The competition between different local hydrogen-bonding environments has been hypothesized as a possible origin of the anomalous properties of liquid water. Through a systematic application of the many-body expansion of the total energy, we demonstrate that the local structure of liquid water at room temperature is determined by a delicate balance between two-body and three-body energies, which is further modulated by higher-order many-body effects. Besides providing fundamental insights into the structure of liquid water, this analysis also emphasizes that a correct representation of two-body and three-body energies requires sub-chemical accuracy that is nowadays only achieved by many-body models rigorously derived from the many-body expansion of the total energy, which thus hold great promise for shedding light on the molecular origin of the anomalous behavior of liquid water. 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.
Bibliography:ab initio
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1-6. Comparisons between radial distribution functions (RDFs) calculated from PIMD simulations with the MB-XC PEFs introduced in this study and the corresponding
clusters with
Electronic supplementary information (ESI) available: Brief overview of the many-body expansion of the total energy and details about the functional form adopted by MB-pol. Additional analyses of many-body effects in (H
10.1039/c9sc03291f
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XC functionals. See DOI
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SC0019490
USDOE Office of Science (SC)
ISSN:2041-6520
2041-6539
DOI:10.1039/c9sc03291f