Many-Body Effects Determine the Local Hydration Structure of Cs+ in SolutionClick to copy article linkArticle link copied!
- Debbie ZhuangDebbie ZhuangDepartment of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United StatesMore by Debbie Zhuang
- Marc RieraMarc RieraDepartment of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United StatesMore by Marc Riera
- Gregory K. SchenterGregory K. SchenterPhysical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United StatesMore by Gregory K. Schenter
- John L. Fulton*John L. Fulton*E-mail: [email protected]Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United StatesMore by John L. Fulton
- Francesco Paesani*Francesco Paesani*E-mail: [email protected]Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United StatesMaterials Science and Engineering, University of California, San Diego, La Jolla, California 92093, United StatesSan Diego Supercomputer Center, University of California, San Diego, La Jolla, California 92093, United StatesMore by Francesco Paesani
Abstract

A systematic analysis of the hydration structure of Cs+ ions in solution is derived from simulations carried out using a series of molecular models built upon a hierarchy of approximate representations of many-body effects in ion–water interactions. It is found that a pairwise-additive model, commonly used in biomolecular simulations, provides poor agreement with experimental X-ray spectra, indicating an incorrect description of the underlying hydration structure. Although the agreement with experiment improves in simulations with a polarizable model, the predicted hydration structure is found to lack the correct sequence of water shells. Progressive inclusion of explicit many-body effects in the representation of Cs+–water interactions as well as accounting for nuclear quantum effects is shown to be necessary for quantitatively reproducing the experimental X-ray spectra. Besides emphasizing the importance of many-body effects, these results suggest that molecular models rigorously derived from many-body expansions hold promise for realistic simulations of aqueous solutions.
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(4)
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(21)
, 9269-9289. https://doi.org/10.1021/acs.jctc.4c01005
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(28)
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(8)
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(42)
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(19)
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(14)
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- Zhuanfang Jing, Yongquan Zhou, Toshio Yamaguchi, Koji Yoshida, Kazutaka Ikeda, Koji Ohara, Guangguo Wang. Hydration of Alkali Metal and Halide Ions from Static and Dynamic Viewpoints. The Journal of Physical Chemistry Letters 2023, 14
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(45)
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(41)
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(24)
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(6)
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(13)
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(4)
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(49)
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(29)
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(2)
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(23)
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(5)
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(5)
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(37)
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(10)
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(1)
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(12)
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(6)
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(43)
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(19)
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(15)
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(14)
https://doi.org/10.1063/5.0002162
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ab initio
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(19)
https://doi.org/10.1063/1.5123999
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(19)
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