Articles written in Pramana – Journal of Physics
Volume 3 Issue 3 September 1974 pp 143-155 Solids
The possibility of writing the repulsive energy in the Born model of binary ionic crystals as a sum of two separate contributions from the two ions has been investigated. Such an approach leads to two identities, one connecting the lattice spacings of a family of ionic crystals and the other connecting their compressibilities. These identities have been tested on the alkali halide crystals over a range of pressures. The agreement is found to be quite satisfactory. Some further predictions with respect to crystals which exist as two polymorphs have also been tested. In all cases, the deviations of the experimental values from the exact identities can be traced to the fact that second neighbour repulsions in the crystals have been neglected. It is hence concluded that individual compressive energies for ions in ionic crystals is a very attractive possibility.
Volume 13 Issue 5 November 1979 pp 559-570 Solids
Ionic radii and compressibilities have been calculated for a number of monovalent and divalent ions and radicals on the basis of the compressible ion theory. In this theory, the compression energy of an ion is given as a two-parameter function of its radius,
Volume 13 Issue 5 November 1979 pp 571-579 Solids
The problem of the relative stability of ionic structures is still unsolved current semi-empirical theories wrongly predict the caesium halides to have the NaCl structure. We point out here that these theories also predict some of the other alkali halides to occur in cubic ZnS structure. To understand these discrepancies, we study the effect of various interactions (such as second neighbour repulsion, van der Waals interaction and differences in ionic compressibilities) on the relative stability of simple structures. The results throw into question the radius ratio approach. It is suggested that one could allow for the presence of three-body interactions by relaxing the requirement that the repulsion interaction should be strictly proportional to the number of neighbours. Such an approach might explain the relative stability of simple ionic structures.
Volume 13 Issue 6 December 1979 pp 581-597 Solids
Ions in ionic crystals are considered to exist in compressible space-filling polyhedral cells analogous to the Wigner-Seitz cell in metals. Repulsion arises from the compression energy of the ions written as a surface integral over the ionic cells. Two adjustable parameters are introduced per ion with the provision that the same parameters can be used in any crystal of any structure in which the ion occurs. The 18 parameters for the 5 alkali and 4 halogen ions have been determined from PV data on the 20 alkali halides. The important successes of the theory are: (i) All the twenty alkali halides are correctly predicted to occur in their observed structures (ii) The thermal transition in CsCl is explained (iii) The pressure transitions in the alkali halides are predicted well (iv) The calculated values of the variation of transition pressures with temperature agree well with experiment. These results are much better than those obtained by earlier theories.
Volume 17 Issue 1 July 1981 pp 13-23 Solid State Physics
A simple theory is developed which shows that the regions of stability of the CsCl, NaCl and ZnS structures can be demarcated in a two-dimensional plot of the radius ratio versus the strength of the van der Waals interaction. There is good agreement with experiment. The effect of pressure on these structures is explained qualitatively. The increased occurrence of the ZnS structure and the decreased stability of the CsCl structure in the A2+ B2− crystals compared to the A+B− crystals is also explained. Finally it is shown that the radius ratio and the polarizabilities of the ions are the important factors that determine the structures of AB2 crystals.
Volume 17 Issue 4 October 1981 pp 327-335 Crystallography
It is suggested that the radio astronomical technique of image reconstruction called
Volume 19 Issue 4 October 1982 pp 367-379 Solid State Physics
The thermal properties of ionic crystals are analysed using the variational principle of classical statistical mechanics. The Einstein and Debye pictures of the lattice vibrations are adopted as trial Hamiltonians. No explicit calculation of the lattice spectrum is needed. The variational result for the thermal expansion in the Einstein picture is identical to that recently derived by Narayan and Ramaseshan by a physically motivated thermal force picture. The agreement with experimental values in the alkali halide family of crystals is surprisingly good, the root mean square error being about 14%. The parameters in the interionic potential used are obtained from the lattice spacings and compressibilities of the crystals and not from anharmonic properties. The Debye picture gives about equally good results for the thermal expansion, but better results for the thermal vibration amplitudes of the ions. It differs from the Einstein picture in incorporating correlated vibrations of atoms and in having an explicit Coulomb contribution to the thermal properties. It is suggested that the theory given in this paper has a useful role to play in studies of thermal expansion and phase stability for large families of ionic crystals when combined with semi-empirical theories.
Volume 21 Issue 5 November 1983 pp 301-309 Solid State Physics
The divalent ions in alkaline earth chalcogenides are viewed as compressible objects and are treated within a purely ionic model. As in earlier studies on the alkali and ammonium halides, the ions are taken to be in the form of space-filling polyhedral cells and the compression energy, which is the source of repulsion, is written as a surface integral over the cell faces. A simple method of computing the repulsion energy in any crystal lattice of arbitrary symmetry is proposed and the repulsion parameters
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