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Title: Electric Field Effects on the Intermolecular Interactions in Water Whiskers: Insight from Structures, Energetics, and Properties

Abstract

Modulation of intermolecular interactions in response to external electric fields could be fundamental to the formation of unusual forms of water, such as water whiskers. However, a detailed understanding of the nature of intermolecular interactions in such systems is lacking. In this study, we present novel theoretical results based on electron correlation calculations regarding the nature of H-bonds in water whiskers, which is revealed by studying their evolution under external electric fields with various field strengths. We find that the water whiskers consisting of 2-7 water molecules all have a chain-length dependent critical electric field. Under the critical electric field, the most compact chain structures are obtained, featuring very strong H-bonds, herein referred to as covalent H-bonds. In the case of a water dimer whisker, the bond length of the novel covalent H-bond shortens by 25%, the covalent bond order increases by 9 times, and accordingly the H-bond energy is strengthened by 5 times compared to the normal H-bond in a (H2O)2 cluster. Below the critical electric field, it is observed that with increasing field strength, H-bonding orbitals display gradual evolutions in the orbital energy, orbital ordering, and orbital nature (i.e., from typical -style orbital to unusual -style double H-bondingmore » orbital). We also show that beyond the critical electric field, a single water whisker may disintegrate to form a loosely bound zwitterionic chain due to a relay-style proton transfer, whereas two water whiskers may undergo intermolecular cross-linking to form a quasi-two-dimensional water network. In conclusion, these results help shed new insight on the effects of electric fields on water whisker formation.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [3]
+ Show Author Affiliations
  1. Jilin Univ., Changchun (China)
  2. South China Normal University, Guangzhou (China)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1265297
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 119; Journal Issue: 10; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bai, Yang, He, Hui-Min, Li, Ying, Zhou, Zhong-Jun, Wang, Jia-Jun, Wu, Di, Chen, Wei, Gu, Feng-Long, Sumpter, Bobby G., and Huang, Jingsong. Electric Field Effects on the Intermolecular Interactions in Water Whiskers: Insight from Structures, Energetics, and Properties. United States: N. p., 2015. Web. doi:10.1021/jp511460c.
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Bai, Yang, He, Hui-Min, Li, Ying, Zhou, Zhong-Jun, Wang, Jia-Jun, Wu, Di, Chen, Wei, Gu, Feng-Long, Sumpter, Bobby G., & Huang, Jingsong. Electric Field Effects on the Intermolecular Interactions in Water Whiskers: Insight from Structures, Energetics, and Properties. United States. https://doi.org/10.1021/jp511460c
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Bai, Yang, He, Hui-Min, Li, Ying, Zhou, Zhong-Jun, Wang, Jia-Jun, Wu, Di, Chen, Wei, Gu, Feng-Long, Sumpter, Bobby G., and Huang, Jingsong. Thu . "Electric Field Effects on the Intermolecular Interactions in Water Whiskers: Insight from Structures, Energetics, and Properties". United States. https://doi.org/10.1021/jp511460c. https://www.osti.gov/servlets/purl/1265297.
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@article{osti_1265297,
title = {Electric Field Effects on the Intermolecular Interactions in Water Whiskers: Insight from Structures, Energetics, and Properties},
author = {Bai, Yang and He, Hui-Min and Li, Ying and Zhou, Zhong-Jun and Wang, Jia-Jun and Wu, Di and Chen, Wei and Gu, Feng-Long and Sumpter, Bobby G. and Huang, Jingsong},
abstractNote = {Modulation of intermolecular interactions in response to external electric fields could be fundamental to the formation of unusual forms of water, such as water whiskers. However, a detailed understanding of the nature of intermolecular interactions in such systems is lacking. In this study, we present novel theoretical results based on electron correlation calculations regarding the nature of H-bonds in water whiskers, which is revealed by studying their evolution under external electric fields with various field strengths. We find that the water whiskers consisting of 2-7 water molecules all have a chain-length dependent critical electric field. Under the critical electric field, the most compact chain structures are obtained, featuring very strong H-bonds, herein referred to as covalent H-bonds. In the case of a water dimer whisker, the bond length of the novel covalent H-bond shortens by 25%, the covalent bond order increases by 9 times, and accordingly the H-bond energy is strengthened by 5 times compared to the normal H-bond in a (H2O)2 cluster. Below the critical electric field, it is observed that with increasing field strength, H-bonding orbitals display gradual evolutions in the orbital energy, orbital ordering, and orbital nature (i.e., from typical -style orbital to unusual -style double H-bonding orbital). We also show that beyond the critical electric field, a single water whisker may disintegrate to form a loosely bound zwitterionic chain due to a relay-style proton transfer, whereas two water whiskers may undergo intermolecular cross-linking to form a quasi-two-dimensional water network. In conclusion, these results help shed new insight on the effects of electric fields on water whisker formation.},
doi = {10.1021/jp511460c},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 10,
volume = 119,
place = {United States},
year = {Thu Feb 19 00:00:00 EST 2015},
month = {Thu Feb 19 00:00:00 EST 2015}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jp511460c
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Cited by: 15 works
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Figures / Tables:

Figure 1 Figure 1: Linear chain structures of water whiskers with 2−7 water molecules, under respective critical electric fields (Fc). The Fc decreases with increasing chain length. The linear chain (n = 2) and cyclic structures (n = 3−5) of typical (H2O)n water clusters are also shown for comparison. All structures weremore » optimized at the level of MP2. The green lines represent the H-bonds whose covalent characteristics were focused in this study. The inset illustrates the atomic and bond labels.« less
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