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Title: 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. H 2P 2O 7 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 P 2O 5 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, indicatingmore » that fundamental understanding remains an open question.« less

Authors:
 [1];  [2];  [3];  [4];  [5]; ORCiD logo [2]
  1. 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
  2. Univ. of Missouri, Columbia, MO (United States). Dept. of Physics and Astronomy
  3. Univ. Ibn Tofail, Kenitra (Morocco). Lab. of Materials Engineering and Environment
  4. Mohammad Univ., Rabat (Morocco). Energie Materiaux et Developpement Durable
  5. 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. doi: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. doi: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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Works referenced in this record:

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996