Unique water H-bonding types on metal surfaces: from the bonding nature to cooperativity rules

Understanding the nature of H-bonding interactions is essential to modern sciences, such as biology, chemistry, and physics. Using density functional theory calculations, herein, we have identified two unique H-bonding types existing in a single sheet of a mixed water–hydroxyl phase on close-packed...

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Main Authors: Jibiao Li, Chang Qing Sun
Format: Article
Language:English
Published: Elsevier 2021-12-01
Series:Materials Today Advances
Subjects:
Online Access:http://www.sciencedirect.com/science/article/pii/S2590049821000424
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spelling doaj-6247ee3f78064384a411b0b4dba0d68f2021-09-29T04:26:40ZengElsevierMaterials Today Advances2590-04982021-12-0112100172Unique water H-bonding types on metal surfaces: from the bonding nature to cooperativity rulesJibiao Li0Chang Qing Sun1Center for Materials and Energy (CME), Chongqing Key Laboratory of Inorganic Special Functional Materials, and Chongqing Key Laboratory of Extraordinary Bond Engineering and Advanced Materials Technology (EBEAM), College of Materials Science and Engineering, Yangtze Normal University, Chongqing, 408100, China; College of Materials Science and Engineering, Chongqing University, Chongqing, 400044, China; Corresponding author.Center for Materials and Energy (CME), Chongqing Key Laboratory of Inorganic Special Functional Materials, and Chongqing Key Laboratory of Extraordinary Bond Engineering and Advanced Materials Technology (EBEAM), College of Materials Science and Engineering, Yangtze Normal University, Chongqing, 408100, China; School of Electrical and Electronic Engineering, Nanyang Technological University, 639798, Singapore; Corresponding author.Understanding the nature of H-bonding interactions is essential to modern sciences, such as biology, chemistry, and physics. Using density functional theory calculations, herein, we have identified two unique H-bonding types existing in a single sheet of a mixed water–hydroxyl phase on close-packed metal surfaces, in sharp contrast to conventional H-bonds in liquid water and water ices. Interestingly, the shallow H-bonds show reduced electrostatic and Pauli repulsion interactions, with an electrostatic polar character resulted from complete σ resonances, whereas the deep H-bonds exhibit enhanced electrostatic and Pauli repulsion interactions, with an electrostatic dipolar feature originated from hybrid orbital interactions. A trade-off-like cooperativity law of the two types of H-bonds was discovered, that is, strengthening in the internal bonds (dO–H) leads to weakening in the external bonds (dO:H) or vice versa. However, the shallow H-bonds exhibit a non-linear cooperativity, whereas the deep H-bonds show a linear cooperativity. We also identified an oxygen backbone cooperativity rule that strengthening the adsorbate–metal interactions has a net effect in analogy to reducing the O–O repulsion within the adlayer. Furthermore, we have discovered several universality classes in geometrical, vibrational, and electronic spaces for the two H-bonding types. Although shared by electronic universality classes, the two contrasting H-bonding types are featured by divergent trends with significant overlapping, where competitive variations in the electrostatic and Pauli repulsion strengths are basic rules for the cooperative H-bonding types. The knowledge of the unconventional H-bonding types expands our current understanding of H-bonding interactions in liquid water and water ices and points to the importance of H-bonding manipulation at electronic levels. These findings not only shed new light on probing the fundamental nature of H-bonds in general but also have insightful implications for resolving the cooperative H-bonding nature of interfacial water, liquid water, water ices, and aqueous solutions.http://www.sciencedirect.com/science/article/pii/S2590049821000424H-bondsWater–hydroxyl phaseSurface water
collection DOAJ
language English
format Article
sources DOAJ
author Jibiao Li
Chang Qing Sun
spellingShingle Jibiao Li
Chang Qing Sun
Unique water H-bonding types on metal surfaces: from the bonding nature to cooperativity rules
Materials Today Advances
H-bonds
Water–hydroxyl phase
Surface water
author_facet Jibiao Li
Chang Qing Sun
author_sort Jibiao Li
title Unique water H-bonding types on metal surfaces: from the bonding nature to cooperativity rules
title_short Unique water H-bonding types on metal surfaces: from the bonding nature to cooperativity rules
title_full Unique water H-bonding types on metal surfaces: from the bonding nature to cooperativity rules
title_fullStr Unique water H-bonding types on metal surfaces: from the bonding nature to cooperativity rules
title_full_unstemmed Unique water H-bonding types on metal surfaces: from the bonding nature to cooperativity rules
title_sort unique water h-bonding types on metal surfaces: from the bonding nature to cooperativity rules
publisher Elsevier
series Materials Today Advances
issn 2590-0498
publishDate 2021-12-01
description Understanding the nature of H-bonding interactions is essential to modern sciences, such as biology, chemistry, and physics. Using density functional theory calculations, herein, we have identified two unique H-bonding types existing in a single sheet of a mixed water–hydroxyl phase on close-packed metal surfaces, in sharp contrast to conventional H-bonds in liquid water and water ices. Interestingly, the shallow H-bonds show reduced electrostatic and Pauli repulsion interactions, with an electrostatic polar character resulted from complete σ resonances, whereas the deep H-bonds exhibit enhanced electrostatic and Pauli repulsion interactions, with an electrostatic dipolar feature originated from hybrid orbital interactions. A trade-off-like cooperativity law of the two types of H-bonds was discovered, that is, strengthening in the internal bonds (dO–H) leads to weakening in the external bonds (dO:H) or vice versa. However, the shallow H-bonds exhibit a non-linear cooperativity, whereas the deep H-bonds show a linear cooperativity. We also identified an oxygen backbone cooperativity rule that strengthening the adsorbate–metal interactions has a net effect in analogy to reducing the O–O repulsion within the adlayer. Furthermore, we have discovered several universality classes in geometrical, vibrational, and electronic spaces for the two H-bonding types. Although shared by electronic universality classes, the two contrasting H-bonding types are featured by divergent trends with significant overlapping, where competitive variations in the electrostatic and Pauli repulsion strengths are basic rules for the cooperative H-bonding types. The knowledge of the unconventional H-bonding types expands our current understanding of H-bonding interactions in liquid water and water ices and points to the importance of H-bonding manipulation at electronic levels. These findings not only shed new light on probing the fundamental nature of H-bonds in general but also have insightful implications for resolving the cooperative H-bonding nature of interfacial water, liquid water, water ices, and aqueous solutions.
topic H-bonds
Water–hydroxyl phase
Surface water
url http://www.sciencedirect.com/science/article/pii/S2590049821000424
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