In this second volume of the Mineralogical Society’s ‘Landmark’ series, Prof. Frank Hawthorne has selected a number of key papers, some of which are true milestones of mineralogy and crystallography, showing the acceleration of research and the increase in knowledge in the field of crystal-chemistry. The papers follow in chronological sequence, allowing the reader to see how crystallography and, particularly, mineralogy have evolved during the last 80 years. He has chosen the papers on the basis of three related aspects: (a) the nature of chemical bonds, and (b) their relation to bond topology, leading to (c) the prediction of bond topologies and their hierarchical organization. His commentaries on the selected papers provided a coherent narrative thread running through the volume. In the first chapter ‘Bond topology and Minerals’, Hawthorne reviews the long history of the mineralogy and crystallography, reporting the evolution of the knowledge and the experimental findings in the last 2,000 years. The author introduces the mathematical concept of topology and how to use this tool for the description of the structural configuration in crystals. In addition, he discusses the motivation of mineralogists for understanding and developing principles of bond topology. In chapter 2, two milestone papers by Linus Pauling (both published in 1929) on the structure of complex ionic crystals are reported and enriched with comments. Chapter 3 is devoted to a further milestone paper for mineralogy written by W.L. Bragg (1930), on the structure classification of the silicate minerals, the isomorphous replacement in silicates and on the application of the Pauling’s rules to this class of minerals. In Chapter 4, we jump to the 1970s with the paper of P.B. Moore (1970) on the stereoisomerism among octahedral and tetrahedral chains. Moore based his study not on a specific mineral structure, but examined the different ways in which polyhedra could link via vertices to form chains. He defines the concept of ‘‘structural hierarchy’’ as a general scheme that ties together a certain number of arrangements. An extension of the structural analysis of Moore is found in chapter 6, which is devoted to his systematic study of edge-sharing clusters, deriving the possible arrangements based solely on topological and geometrical principles according to the notions of energy minima and stability (Moore 1974). Chapter 5 deals with the paper by Brown and Shannon (1973), on the empirical bond-valence/ bond-length curves for oxides. A further refinement of the Brown and Shannon approach, into a comprehensive theory that addresses many aspects of the chemical bonding, was developed by Brown (1981), and is presented in chapter 8. Bond-valence analysis of inorganic crystal structures is an essential check on the validity of any structure determination. In his commentary on chapter 8, Hawthorne outlines the critical points introduced by Brown in the bond-valence theory, with interesting application in mineralogy, and presents the bond-valence theory as a molecular orbital theory and as an ionic theory. Chapter 7 is devoted to the paper by L.S. Dent Glasser (1979) on non-existent silicates, emphasizing that the observed arrangements in silicates represent only a small fraction of those topologically possible. Chapter 9 deals with the paper of Hawthorne (1983) on the graphical enumeration of polyhedral clusters. The author developed a ‘‘structural hierarchy’’ hypothesis which has an energetic basis and relates to paragenetic sequences. An example is Bowen’s reaction series shown as a function of the polymerization characteristic of the structure involved. A related topic is covered in chapter 10, which discusses the energetic content of bond topology with reference to the paper by Burdett et al. (1984). The last paper of this collection constituting chapter 11 is devoted to the role of OH and H2O in oxide and oxysalt minerals, based on Hawthorne (1992). The author analysed the roleplayed by (OH) , (H2O)0, (H3O)+ and (H5O2)2+ in controlling bonding topology, topological dimensionality and the role of H2O as a bond-valence transformer, which bears on the, often highly selective, uptake of interstitial cations by environmentally significant minerals. Chapter 12 is the coda, focusing on the prediction of bond topology and of the stoichiometry of stable compounds in a given chemical system. I think that the re-publication of these landmark papers, accompanied by the commentaries of Prof. Hawthorne, will be useful not only for undergraduate or PhD students, but for all structural mineralogists. This collection provides valuable insights into the evolution of structural mineralogy and its wider application to the petrology. As several of the milestone papers collected in this book are published in German journals (Zeitschrift fu¨r Kristallographie, Neues Jahrbuch fu¨r Mineralogie Monatshefte), I did a little inquiry and I found that these journals are often not readily available in departmental libraries, and so this is another good reason to have this book in your own library. In conclusion, I warmly recommend this volume to all mineralogists and to Earth sciences libraries. G. DIEGO GATTA

F.C. Hawthorne, Landmark papers : structure topology [Recensione] / G.D. Gatta. - In: MINERALOGICAL MAGAZINE. - ISSN 0026-461X. - 71:6(2007), pp. 745-746.

F.C. Hawthorne, Landmark papers : structure topology

G.D. Gatta
Primo
2007

Abstract

In this second volume of the Mineralogical Society’s ‘Landmark’ series, Prof. Frank Hawthorne has selected a number of key papers, some of which are true milestones of mineralogy and crystallography, showing the acceleration of research and the increase in knowledge in the field of crystal-chemistry. The papers follow in chronological sequence, allowing the reader to see how crystallography and, particularly, mineralogy have evolved during the last 80 years. He has chosen the papers on the basis of three related aspects: (a) the nature of chemical bonds, and (b) their relation to bond topology, leading to (c) the prediction of bond topologies and their hierarchical organization. His commentaries on the selected papers provided a coherent narrative thread running through the volume. In the first chapter ‘Bond topology and Minerals’, Hawthorne reviews the long history of the mineralogy and crystallography, reporting the evolution of the knowledge and the experimental findings in the last 2,000 years. The author introduces the mathematical concept of topology and how to use this tool for the description of the structural configuration in crystals. In addition, he discusses the motivation of mineralogists for understanding and developing principles of bond topology. In chapter 2, two milestone papers by Linus Pauling (both published in 1929) on the structure of complex ionic crystals are reported and enriched with comments. Chapter 3 is devoted to a further milestone paper for mineralogy written by W.L. Bragg (1930), on the structure classification of the silicate minerals, the isomorphous replacement in silicates and on the application of the Pauling’s rules to this class of minerals. In Chapter 4, we jump to the 1970s with the paper of P.B. Moore (1970) on the stereoisomerism among octahedral and tetrahedral chains. Moore based his study not on a specific mineral structure, but examined the different ways in which polyhedra could link via vertices to form chains. He defines the concept of ‘‘structural hierarchy’’ as a general scheme that ties together a certain number of arrangements. An extension of the structural analysis of Moore is found in chapter 6, which is devoted to his systematic study of edge-sharing clusters, deriving the possible arrangements based solely on topological and geometrical principles according to the notions of energy minima and stability (Moore 1974). Chapter 5 deals with the paper by Brown and Shannon (1973), on the empirical bond-valence/ bond-length curves for oxides. A further refinement of the Brown and Shannon approach, into a comprehensive theory that addresses many aspects of the chemical bonding, was developed by Brown (1981), and is presented in chapter 8. Bond-valence analysis of inorganic crystal structures is an essential check on the validity of any structure determination. In his commentary on chapter 8, Hawthorne outlines the critical points introduced by Brown in the bond-valence theory, with interesting application in mineralogy, and presents the bond-valence theory as a molecular orbital theory and as an ionic theory. Chapter 7 is devoted to the paper by L.S. Dent Glasser (1979) on non-existent silicates, emphasizing that the observed arrangements in silicates represent only a small fraction of those topologically possible. Chapter 9 deals with the paper of Hawthorne (1983) on the graphical enumeration of polyhedral clusters. The author developed a ‘‘structural hierarchy’’ hypothesis which has an energetic basis and relates to paragenetic sequences. An example is Bowen’s reaction series shown as a function of the polymerization characteristic of the structure involved. A related topic is covered in chapter 10, which discusses the energetic content of bond topology with reference to the paper by Burdett et al. (1984). The last paper of this collection constituting chapter 11 is devoted to the role of OH and H2O in oxide and oxysalt minerals, based on Hawthorne (1992). The author analysed the roleplayed by (OH) , (H2O)0, (H3O)+ and (H5O2)2+ in controlling bonding topology, topological dimensionality and the role of H2O as a bond-valence transformer, which bears on the, often highly selective, uptake of interstitial cations by environmentally significant minerals. Chapter 12 is the coda, focusing on the prediction of bond topology and of the stoichiometry of stable compounds in a given chemical system. I think that the re-publication of these landmark papers, accompanied by the commentaries of Prof. Hawthorne, will be useful not only for undergraduate or PhD students, but for all structural mineralogists. This collection provides valuable insights into the evolution of structural mineralogy and its wider application to the petrology. As several of the milestone papers collected in this book are published in German journals (Zeitschrift fu¨r Kristallographie, Neues Jahrbuch fu¨r Mineralogie Monatshefte), I did a little inquiry and I found that these journals are often not readily available in departmental libraries, and so this is another good reason to have this book in your own library. In conclusion, I warmly recommend this volume to all mineralogists and to Earth sciences libraries. G. DIEGO GATTA
Book Review
Settore GEO/09 - Georisorse Miner.Appl.Mineral.-Petrogr.per l'amb.e i Beni Cul
2007
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