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Another look at the structure of the (H2O)n•־ system: water anion vs. hydrated electron

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Abstract

Quantum chemical computations using both density functional theory and coupled-cluster theory methods, in conjunction with a polarizable continuum model for treatment of structures in solution, were carried out on a series of small water anions [(H2O)n]•־, n = 2, 3, 4, 5, and 16. Location of the excess electron was probed from a partition of electron densities using ELF and AIM techniques. For each size n of the [(H2O)n]•־ system, two distinct structural motifs are identified: a classical water radical anion formed by hydrogen bonds and a hydrated electron in which the excess electron is directly interacting with H atoms. Both motifs have comparable energy content and likely coexist in aqueous solution.

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Acknowledgments

MTN is grateful to Prof. Andreas Savin at Universite Sorbonne Paris for valuable discussion on the ELF computation in solution.

Funding

TLH and MTN thank Ton Duc Thang University (Demasted) for support. JL and DM acknowledge the support of NSF-CREST (Award No. 154774).

Author information

Authors and Affiliations

  1. Computational Chemistry Research Group, Ton Duc Thang University, Ho Chi Minh City, Vietnam

    Trinh Le Huyen & Minh Tho Nguyen

  2. Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam

    Trinh Le Huyen & Minh Tho Nguyen

  3. Institute for Computational Science and Technology (ICST), Ho Chi Minh City, Vietnam

    Long Van Duong

  4. Interdisciplinary Center for Nanotoxicity, Department of Chemistry, Physics and Atmospheric Sciences, Jackson State University, Jackson, MS, 39217, USA

    Devashis Majumdar & Jerzy Leszczynski

Authors
  1. Trinh Le Huyen
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  2. Long Van Duong
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  3. Devashis Majumdar
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  4. Jerzy Leszczynski
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  5. Minh Tho Nguyen
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Contributions

All authors contributed to the study conception and calculations design. TLH and LVD carried out quantum chemical computations and data collection. The first draft of the manuscript was written by MTN and edited by DM and JL, and all authors commented on the analyses and the text.

Corresponding author

Correspondence to Minh Tho Nguyen.

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The authors declare no competing interests.

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Supplementary information

Figures display and Tables list Cartesian coordinates of, the optimized structures of various anionic water oligomers.

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Le Huyen, T., Van Duong, L., Majumdar, D. et al. Another look at the structure of the (H2O)n•־ system: water anion vs. hydrated electron. Struct Chem 32, 655–665 (2021). https://doi.org/10.1007/s11224-021-01749-3

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  • DOI: https://doi.org/10.1007/s11224-021-01749-3

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