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Extreme Conditions

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Introduction to Structural Chemistry

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Abstract

This chapter is mainly devoted to structural studies under static or dynamic high pressure (HP), which allows much more drastic change of crystal structure and bonding than variations of temperature. The ‘workhorse’ of static HP crystallography is the diamond anvil cell, producing hydrostatic pressure of up to 300 GPa, albeit in a very small volume. Dynamic pressure produced by chemical explosives, electric discharge, projectile impact or irradiation, is much higher but of very short duration—unexpectedly, sufficient for phase transitions and crystallization! A combined dynamic-static technique has been developed. A bewildering variety of HP polymorphs have been discovered; their systematic survey shows a general increase of coordination number with pressure, including transformations of molecular into polymeric structures, and of crystals into amorphous solids. Dynamic compression also produced some unusual phase transitions with a decrease (!) of density, explained by high concentration of defects, and dissociation of compounds into elements. ‘Polyamorphous’ transitions (glass-glass, or liquid-liquid), usually gradual, can also be surprisingly abrupt. Away from phase transitions, compression of solids is described by equations of state, which are critically reviewed here.

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Notes

  1. 1.

    To the authors’ knowledge, studies of detonation diamond in the USSR were going on since 1960’s but were kept secret. However, we believe that in the absence of any open publications prior to 1988, any attempts to re-establish the scientific priority now are pointless

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Authors and Affiliations

  1. Institute of Structural Macrokinetics and Materials Science, Russian Academy of Sciences, Academician Osipyan str. 8, 142432, Chernogolovka, Moscow Region, Russia

    Prof. Stepan S. Batsanov

  2. Chemistry Department, Durham University, Science Site, South Road, DH1 3LE, Durham, United Kingdom

    Andrei S. Batsanov Ph.D.

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Correspondence to Stepan S. Batsanov .

Appendix

Appendix

10.1.1 Supplementary Tables

Compilations of EOSs are available in [10.1–10.5]; these values of В о and В о ′ are given without references, data from other sources are given with references.

Table S10.1 Bulk moduli (GPа) and pressure derivatives of the MX compounds
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Table S10.2 Bulk moduli (GPа) and pressure derivatives of the MX2 hydrides, halides, oxides and chalcogenides
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Table S10.3 Bulk moduli (GPа) and pressure derivatives of the MX3 hydrides, halides, and hydroxides
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Table S10.4 Bulk moduli (GPа) and pressure derivatives for binary oxides of the MnOm type
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Table S10.5 Bulk moduli (GPа) and pressure derivatives for binary nitrides
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Table S10.6 Bulk moduli (GPа) and pressure derivatives for binary borides
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Table S10.7 Bulk moduli (GPа) and pressure derivatives for binary carbides and silicides
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Table S10.8 Bulk moduli (GPа) and pressure derivatives for binary phosphides and arsenides
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Table S10.9 Bulk moduli (GPа) and pressure derivatives for ternary oxides
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Table S10.10 Bulk moduli (GPа) and pressure derivatives for molecular substances and polymers. (Experimental data from review [5.354], except where specified)
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Table S10.11 Characteristics of polymorphous modifications of elements and MX compounds
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Table S10.12 Characteristics of polymorphous modifications of MX2 compounds
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Table S10.13 Bulk moduli (GPa) of elements аt different temperatures (K)
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Table S10.14 Coefficients in the Hugoniot equation of elements; c in km/s [10.204]
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Table S10.15 Coefficients in Hugoniot equations for molecular compounds; c in km/s [10.205]
Full size table

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Batsanov, S., Batsanov, A. (2012). Extreme Conditions. In: Introduction to Structural Chemistry. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-4771-5_10

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