Atomic-Scale Understanding of Structure and Properties of Complex Pyrophosphate Crystals by First-Principles Calculations

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.

[1]  W. Ching,et al.  Ab Initio Modeling of Structure and Properties of Single and Mixed Alkali Silicate Glasses. , 2017, The journal of physical chemistry. A.

[2]  G. Schleinzer,et al.  Gallium phosphate, GaPO4: a new piezoelectric crystal material for high-temperature sensorics , 1997 .

[3]  W. Ching,et al.  Electronic structure, bonding, charge distribution, and x-ray absorption spectra of the (001) surfaces of fluorapatite and hydroxyapatite from first principles , 2007 .

[4]  Y. C. Ratnakaram,et al.  Fluorescence characteristics of Nd3+ doped multicomponent fluoro-phosphate glasses for potential solid-state laser applications , 2016 .

[5]  Richard M. Martin,et al.  First-Principles Calculation of Stress , 1983 .

[6]  W. Ching,et al.  Theoretical investigation of C-(A)-S-H(I) cement hydrates , 2018, Construction and Building Materials.

[7]  R. Powell,et al.  Optical Absorption and Vacuum-Ultraviolet Reflectance of GaN Thin Films , 1970 .

[8]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[9]  A. Reuss,et al.  Berechnung der Fließgrenze von Mischkristallen auf Grund der Plastizitätsbedingung für Einkristalle . , 1929 .

[10]  F. Westheimer.  Why nature chose phosphates. , 1987, Science.

[11]  Ionic Conduction in Phosphate Glasses , 1991 .

[12]  M. Witko,et al.  Electronic structure of vanadyl pyrophosphate: cluster model studies , 2001 .

[13]  R. Khaoulaf,et al.  Vibrational Study of Dipotassium Zinc Bis(Dihydrogendiphosphate) Dihydrate, K2ZN(H2P2O7)2·2H2O , 2012 .

[14]  H. Ez‐zahraouy,et al.  Complex interplay of interatomic bonding in a multi-component pyrophosphate crystal: K2Mg (H2P2O7)2·2H2O , 2017, Royal Society Open Science.

[15]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[16]  Quanmao Yu,et al.  Luminescence properties of phosphate phosphor Ba3Y(PO4)3:Sm3+ , 2015 .

[17]  A. Misra,et al.  Atomic-Scale Quantification of Interfacial Binding between Peptides and Inorganic Crystals: The Case of Calcium Carbonate Binding Peptide on Aragonite , 2017 .

[18]  Wai-Yim Ching,et al.  Ab Initio Calculation of Elastic Constants of Ceramic Crystals , 2007 .

[19]  D. G. Thomas,et al.  Fine Structure and Magneto-Optic Effects in the Exciton Spectrum of Cadmium Sulfide , 1961 .

[20]  I. Tanaka,et al.  First‐principles study in an inter‐granular glassy film model of silicon nitride , 2018 .

[21]  E. Kane,et al.  The valence band structure of the III–V compounds☆ , 1962 .

[22]  S. Kochetkov,et al.  Interaction of HIV-1 Reverse Transcriptase and T7 RNA Polymerase with Phosphonate Analogs of NTP and Inorganic Pyrophosphate , 2001, Molecular Biology.

[23]  V. Valentini,et al.  Crystal structure and vibrational spectroscopy of the new acidic diphosphate (NH4)2Zn(H2P2O7)2 · 2 H2O , 2005 .

[24]  A. Varshneya,et al.  Molar volume and elastic properties of multicomponent chalcogenide glasses , 1991 .

[25]  Bo Peng,et al.  Luminescence in the fluoride-containing phosphate-based glasses: A possible origin of their high resistance to nanosecond pulse laser-induced damage , 2015, Scientific Reports.

[26]  Xiujian Zhao,et al.  Structure and Electronic Properties of a Continuous Random Network Model of an Amorphous Zeolitic Imidazolate Framework (a-ZIF) , 2016 .

[27]  D. N. Waters,et al.  On the Elastic Constants and Structure of the Pure Inorganic Oxide Glasses , 1983, June 16.

[28]  R. French,et al.  Implication of the solvent effect, metal ions and topology in the electronic structure and hydrogen bonding of human telomeric G-quadruplex DNA. , 2016, Physical chemistry chemical physics : PCCP.

[29]  P. York,et al.  The relationship between Young's modulus of elasticity of organic solids and their molecular structure , 1991 .

[30]  Robert S. Mulliken,et al.  Electronic Population Analysis on LCAO–MO Molecular Wave Functions. II. Overlap Populations, Bond Orders, and Covalent Bond Energies , 1955 .

[31]  Paul C. Martin.  Sum Rules, Kramers-Kronig Relations, and Transport Coefficients in Charged Systems , 1967 .

[32]  W. Ching,et al.  Electronic structure and bonding in calcium apatite crystals: Hydroxyapatite, fluorapatite, chlorapatite, and bromapatite , 2004 .

[33]  R. Hill.  The Elastic Behaviour of a Crystalline Aggregate , 1952 .

[34]  W. Ching,et al.  Ab initio simulation of elastic and mechanical properties of Zn- and Mg-doped hydroxyapatite (HAP). , 2015, Journal of the mechanical behavior of biomedical materials.

[35]  W. Cheng,et al.  Crystal and Band Structures, Bonding, and Optical Properties of Solid Compounds of Alkaline Indium (III) Pyrophosphates MInP2O7 (M = Na, K, Rb, Cs) , 2004 .

[36]  Yanchun Zhou,et al.  Ab initio computations of electronic, mechanical, lattice dynamical and thermal properties of ZrP2O7 , 2014 .

[37]  N. H. Leeuw,et al.  Computational studies of phosphate clusters and bioglasses , 2011 .

[38]  R. Khaoulaf,et al.  Structure and Vibrational Spectra of a New Acidic Diphosphate K2Cu(H2P2O7)2·2H2O , 2013 .

[39]  D. Marple,et al.  Electron Effective Mass in ZnSe , 1964 .

[40]  Pamela Habibovic,et al.  Calcium phosphates in biomedical applications: materials for the future? , 2016 .

[41]  Martin Ostoja-Starzewski,et al.  Universal elastic anisotropy index. , 2008, Physical review letters.

[42]  W. Ching,et al.  Electronic Structure Methods for Complex Materials: The orthogonalized linear combination of atomic orbitals , 2012 .

[43]  J. Knowles.  Phosphate based glasses for biomedical applications , 2003 .

[44]  W. Cheng,et al.  Crystal and Band Structures, Bonding, and Optical Properties of Solid Compounds of Alkaline Indium(III) Pyrophosphates MInP2O7 (M: Na, K, Rb, Cs). , 2004 .

[45]  N. Steinmetz,et al.  Impact of Hydrogen Bonding in the Binding Site between Capsid Protein and MS2 Bacteriophage ssRNA. , 2017, The journal of physical chemistry. B.

[46]  W. Ching,et al.  Mechanical properties, electronic structure and bonding of alpha- and beta-tricalcium phosphates with surface characterization. , 2010, Acta biomaterialia.

[47]  R. G. Wheeler,et al.  Exciton Structure and Zeeman Effects in Cadmium Selenide , 1961 .

[48]  W. Ching,et al.  Deformation behavior of an amorphous zeolitic imidazolate framework - from a supersoft material to a complex organometallic alloy. , 2018, Physical chemistry chemical physics : PCCP.

[49]  W. Ching,et al.  Structure and properties of hydrogrossular mineral series , 2017 .

[50]  A. Durif,et al.  Crystal Chemistry of Condensed Phosphates , 1995 .

[51]  W. Ching,et al.  Understanding the atomic and electronic origin of mechanical property in thaumasite and ettringite mineral crystals , 2018, Journal of the American Ceramic Society.

[52]  W. Ching,et al.  Understanding the atomistic origin of hydration effects in single and mixed bulk alkali-silicate glasses , 2018, Journal of the American Ceramic Society.

[53]  Ki Tae Nam,et al.  Coordination tuning of cobalt phosphates towards efficient water oxidation catalyst , 2015, Nature Communications.

[54]  S. Pugh.  XCII. Relations between the elastic moduli and the plastic properties of polycrystalline pure metals , 1954 .

[55]  G. Knoll.  Radiation detection and measurement , 1979 .

[56]  Richard K. Brow,et al.  Review: the structure of simple phosphate glasses , 2000 .

[57]  A. Moliterni,et al.  Synthesis, X-ray crystal structure and vibrational spectroscopy of the acidic pyrophosphate KMg0.5H2P2O7·H2O , 2003 .

[58]  R. S. Mulliken.  Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I , 1955 .

[59]  John E. Nafe,et al.  The Bulk Modulus–Volume Relationship for Oxide Compounds and Related Geophysical Problems , 2013 .