Atomic-Scale Understanding of Structure and Properties of Complex Pyrophosphate Crystals by First-Principles Calculations
Abstract
The electronic structure and mechanical and optical properties of five pyrophosphate crystals with very complex structures are studied by first principles density functional theory calculations. The results show the complex interplay of the minor differences in specific local structures and compositions can result in large differences in reactivity and interaction that are rare in other classes of inorganic crystals. These are discussed by dividing the pyrophosphate crystals into three structural units. H2P2O7 is the most important and dominating unit in pyrophosphates. The other two are the influential cationic group with metals and water molecules. The strongest P-O bond in P2O5 is the strongest bond for crystal cohesion, but O-H and N-H bonds also play an important part. Different type of bonding between O and H atoms such as O-H, hydrogen bonding, and bridging bonds are present. Metallic cations such as Mg, Zn, and Cu form octahedral bonding with O. The water molecule provides the unique H∙∙∙O bonds, and metallic elements can influence the structure and bonding to a certain extent. The two Cu-containing phosphates show the presence of narrow metallic bands near the valence band edge. All this complex bonding affects their physical properties, indicating that fundamental understanding remains anmore »
- Authors:
-
[2]
- Mohammed V Univ., Rabat (Morocco). Faculty of Sciences, Lab. of Spectroscopy, Molecular Modeling, Materials, Nanomaterials, Water and Environment; Univ. Mohammed, Rabat (Morocco). Lab. of Condensed Matter and Interdisciplinary Sciences, Faculty of Sciences
- Univ. of Missouri, Columbia, MO (United States). Dept. of Physics and Astronomy
- Univ. Ibn Tofail, Kenitra (Morocco). Lab. of Materials Engineering and Environment
- Mohammad Univ., Rabat (Morocco). Energie Materiaux et Developpement Durable
- Univ. Mohammed, Rabat (Morocco). Lab. of Condensed Matter and Interdisciplinary Sciences, Faculty of Sciences
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1530864
- Grant/Contract Number:
- AC03-76SF00098
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Applied Sciences
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 5; Journal ID: ISSN 2076-3417
- Publisher:
- MDPI
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS; Pyrophosphate; electronic structure; mechanical properties; optical properties; first-principles calculations
Citation Formats
Khaoulaf, Redouane, Adhikari, Puja, Harcharras, Mohamed, Brouzi, Khalid, Ez-Zahraouy, Hamid, and Ching, Wai-Yim. Atomic-Scale Understanding of Structure and Properties of Complex Pyrophosphate Crystals by First-Principles Calculations. United States: N. p., 2019.
Web. doi:10.3390/app9050840.
Khaoulaf, Redouane, Adhikari, Puja, Harcharras, Mohamed, Brouzi, Khalid, Ez-Zahraouy, Hamid, & Ching, Wai-Yim. Atomic-Scale Understanding of Structure and Properties of Complex Pyrophosphate Crystals by First-Principles Calculations. United States. https://doi.org/10.3390/app9050840
Khaoulaf, Redouane, Adhikari, Puja, Harcharras, Mohamed, Brouzi, Khalid, Ez-Zahraouy, Hamid, and Ching, Wai-Yim. Wed .
"Atomic-Scale Understanding of Structure and Properties of Complex Pyrophosphate Crystals by First-Principles Calculations". United States. https://doi.org/10.3390/app9050840. https://www.osti.gov/servlets/purl/1530864.
@article{osti_1530864,
title = {Atomic-Scale Understanding of Structure and Properties of Complex Pyrophosphate Crystals by First-Principles Calculations},
author = {Khaoulaf, Redouane and Adhikari, Puja and Harcharras, Mohamed and Brouzi, Khalid and Ez-Zahraouy, Hamid and Ching, Wai-Yim},
abstractNote = {The electronic structure and mechanical and optical properties of five pyrophosphate crystals with very complex structures are studied by first principles density functional theory calculations. The results show the complex interplay of the minor differences in specific local structures and compositions can result in large differences in reactivity and interaction that are rare in other classes of inorganic crystals. These are discussed by dividing the pyrophosphate crystals into three structural units. H2P2O7 is the most important and dominating unit in pyrophosphates. The other two are the influential cationic group with metals and water molecules. The strongest P-O bond in P2O5 is the strongest bond for crystal cohesion, but O-H and N-H bonds also play an important part. Different type of bonding between O and H atoms such as O-H, hydrogen bonding, and bridging bonds are present. Metallic cations such as Mg, Zn, and Cu form octahedral bonding with O. The water molecule provides the unique H∙∙∙O bonds, and metallic elements can influence the structure and bonding to a certain extent. The two Cu-containing phosphates show the presence of narrow metallic bands near the valence band edge. All this complex bonding affects their physical properties, indicating that fundamental understanding remains an open question.},
doi = {10.3390/app9050840},
journal = {Applied Sciences},
number = 5,
volume = 9,
place = {United States},
year = {2019},
month = {2}
}
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