Abstract
Structural and dynamical properties of superionic conductors AgI and CuI are studied using molecular dynamics (MD) techniques. Our model of these superionic conductors is based on the use of effective pair potentials. To determine the constants in these potentials, cohesive energy and bulk modulus are used as input; in addition one uses notions of ionic size based on the known crystal structure.
Salient features of the MD technique are outlined. Methods of treating long range Coulomb forces are discussed in detail. This includes the manner of doing Ewald sum for MD cells of arbitrary shape. Features which can be incorporated to expedite the MD calculations are also discussed.
A novel MD technique which allows for a dynamically controlled variation of the shape and size of the MD cell is described briefly. The development of this novel technique has made it possible to study structural phase transitions in superionic conductors. For α-AgI, among the structural properties we have studied are: partial pair correlation functions, mean square displacements of iodines, cation density maps, Havens ratio, etc. The dynamical properties examined include cation self-diffusion, nature of cation jumps, bias in successive jumps, velocity auto correlation functions, current-current correlation functions.
In CuI, we have examined the microscopic nature of γ→α transition. It is found that at about 700 K the copper ions undergo an order-disorder transformation leading to a specific heat anomaly. The nature of the first-order transition and its precursor effects are also analyzed. Results for a number of other structural and dynamical properties for α-CuI are presented.
In AgI the α⇆β transition is studied using the new MD technique. In our model, upon heating β-AgI, the iodines undergo hcp→bcc transformation and the silver ions become mobile, whereas the reverse transformation is observed on cooling α-AgI.
Work supported by the U.S. Department of Energy.
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References
C. Tubandt and E. Lorenz, Z. Physik, Chem. 87, 513 (1914).
K. Funke, Prog. Solid State Chem. 11, 345 (1976).
G.D. Mahan and W.L. Roth (Eds.), Superionic Conductors, Plenum, New York, 1976.
S. Geller (Ed.), Solid Electrolytes, Springer-Verlag, New York, 1977.
P. Hagenmuller and W. Van Gool (Eds.), Solid Electrolytes, Academic Press, New York, 1978.
M.B. Salamon (Ed.), Physics of Superionic Conductors, Springer-Verlag, New York, 1979.
J.B. Boyce and B.A. Huberman, Physics Reports, 51, 190 (1979).
P. Vashishta, J.N. Mundy and G.K. Shenoy (Eds.), Fast Ion Transport in Solids, Elsevier North-Holland, New York, 1979.
W.F. Flygare and R.A. Huggins, J. Phys. Chem. Solids 34, 1119 (1973).
W. Schommers, Phys. Rev. Letters 38, 1536 (1977).
W. Buhrer, R.M. Nicklow and P. Bruesch, Phys. Rev. B17, 3362 (1978).
W. Andreoni and J.C. Phillips, Phys. Rev. B, to be published.
P. Vashishta and A. Rahman, Phys. Rev. Letters 40, 1337 (1978).
P. Vashishta and A. Rahman, in Fast Ion Transport in Solids (Eds., P. Vashishta, J.N. Mundy and G.K. Shenoy ), Elsevier North-Holland, 1979, p. 527.
L. Pauling, The Nature of the Chemical Bond, Cornell University Press, Ithaca, New York, 1960.
L.W. Strock, Z. Physik. Chemie B25, 411 (1934); B31, 132 (1936).
G. Burley, J. Phys. Chem. Solids 25, 629 (1964).
P. Vashishta and A. Rahman, in Third International Meeting on Solid Electrolytes-Solid State Ionics and Galvanic Cells, Sept. 15–19, 1980, Tokyo Japan, Extended Abstracts, p. 187.
P. Vashishta, Bull. Am. Phys. Soc. 26, 372 (1981).
M. Parrinello and A. Rahman, Phys. Rev. Letters 45, 1196 (1980).
M. Parrinello, A. Rahman and P. Vashishta, to be published.
A. Rahman, in Correlation Functions and Quasiparticle Interactions in Condensed Matter (Ed. J. Woods Halley, Plenum, 1977 ), p. 417.
L. Verlet, Phys. Rev. 159, 98 (1967).
C.W. Gear, ANL Report No. 7126, Argonne National Laboratory (1966); Numerical Initial Value Problem in Ordinary Differential Equations, Prentice Hall, Englewood Cliffs, N.J., 1971.
A. Rahman and F. Stillinger, J. Chem. Phys. 55, 3336 (1971).
J.D. Weeks, D. Chandler and H.C. Andersen, J. Chem. Phys. 54, 5237 (1971); 55, 5422 (1971).
R.W. Hockney, S.P. Goel and J.W. Eastwood, Chem. Phys. Letters 21, 589 (1973).
M. Mandell, J. Statistical Physics 15, 299 (1976).
S.W. de Leeuw, J.W. Perram and E.R. Smith, Proc. R. Soc. Lond. A373, 27 (1980); A373, 57 (1980).
K. Singer’s method has been explained in detail in, M.J.L. Sangster and M. Dixon, Adv. in Physics 25, 247 (1976).
M. Parrinello and A. Rahman have evaluated Ewald Sums for arbitrary shaped MD cells in their study of polymorphic transitions in alkali halides using the method of Ref. 20.
S. Brawer (Private Communication). Also see J. Chem. Phys. 72, 4264 (1980).
T. Soules, J. Chem. Phys. 72, 6314 (1980).
Y. Hiwatari and A. Ueda, in Third International Meeting on Solid Electrolytes - Solid State Ionics and Galvanic Cells, Sept. 15–19, 1980, Tokyo, Japan, Extend Abstracts, p. 202; see also A. Fukumoto, Y. Hiwatari and A. Ueda, p. 205.
Y. Tsuchiya, S. Tamaki and Y. Waseda, J. Phys. C: Solid State Phys. 12, 5361 (1979);
R.J. Cava and D.B. McWhan, Phys. Rev. Letters 15, 2046 (1980).
C. Kittel, Introduction to Solid State Physics, Wiley, New York, 1971.
A. Kvist and R. Tarneberg, Z. Naturforsch. 25A, 257 (1970).
R. J. Cava, F. Reidinger and B. J. Wuensch, Solid State Commun. 24, 411 (1977).
G. Jacucci and A. Rahman, J. Chem. Phys. 69, 4117 (1978).
L. Lebowitz, J.K. Percus and L. Verlet, Phys. Rev. 153, 250 (1967); see also W.C. Kerr, Phys. Rev. B19, 5773 (1979).
R.K. Dejus, K. Sköld and B. Graneli, Solid State Ionics, 1, 327 (1980).
K. Miyake, S. Hoshino and T. Takenaka, J. Phys. Soc. Japan 7, 19 (1952); Errata 7, 339 (1952).
A. Rahman and P. Vashishta, using MD trajectories for CuI the intensities of X-ray lines is calculated. The results are in good agreement with Ref. 42.
A. Rahman, J. Chem. Phys. 65, 4585 (1976);
M. Dixon and M. Gillan, J. Phys. C 11, L165 (1978).
A. Rahman, in Fast Ion Transport in Solids (Eds. P. Vashishta, J.N. Mundy and G.K. Shenoy ), Elsevier North-Holland, 1979, p. 643.
A. Rahman, Phys. Rev. 136, A405 (1964).
M. O’Keeffee, in Superionic Conductors (Eds. G.D. Mahan and W.L. Roth ), Plenum, New York, 1976, p. 101.
K. Funke, in Festkorperprobleme (Advances in Solid State Physics), XX, 1 (Ed. J. Treusch ), Vieweg, Braumschweig, 1980.
P.A. Eaglestaff, An Introduction to the Liquid State, Academic Press, London, 1967.
J.Y. Hansen and I.R. McDonald, Theory of Simple Liquids, Academic Press, London, 1976.
A. Rahman, K. Sköld, C. Pelizzari, S.K. Sinha and H.E. Flotow, Phys. Rev. B14, 3630 (1976);
C.J. Glinka, J.M. Rowe, J.J. Rush, A. Rahman, S.K. Sinha and H.E. Flotow, Phys. Rev. B17, 488 (1978).
K. Kompaan and Y. Haven, Trans. Faraday Soc. 52, 786 (1956); 54, 1498 (1958).
P. Jordan and M. Pochon, Helv. Phys. Acta 30, 33 (1957).
I. Yokota, J. Phys. Soc. Japan 21, 420 (1966);
H. O. Kazaki, J. Phys. Soc. Japan 23, 355 (1967).
B.L. Davis and L.H. Adams, Science 146, 519 (1964).
W.A. Bassett, T. Takahashi, Am. Geophys. Union. Trans. 45, 121 (1964).
P.W. Bridgman, Proc. Am. Acad. Arts Sci. 51, 55 (1915).
G.J. Piermarini and C.E. Weir, J. Res. Natl. Bur. Stds. 66A, 325 (1962).
B.M. Riggleman and H.G. Drickamer, J. Chem. Phys. 38, 2721 (1963).
B.-E. Mellander, A. Lunden and M. Friesel, in International Conference on Fast Ionic Transport in Solids, May 18–22, 1981, Gatlinburg, Tennessee, U.S.A., Extended Abstracts, p. 258.
H.C. Andersen, J. Chem. Phys. 72, 2384 (1980).
J.B. Boyce and T. Hayes, in Physics of Superionic Conductors (Ed. M.B. Salamon ), Springer-Verlag, New York, 1979.
T. Hayes and J.B. Boyce, J. Phys. C: Solid St. Phys. 13, L731 (1980).
G.D. Mahan, in Superionic Conductors (Eds. G.D. Mahan and W.L. Roth ), Plenum, New York, 1976, p. 115.
H.U. Beyeler, P. Bruesch, L. Pietronero, W.R. Schneider, S. Strassler and H.R. Zeller, in Physics of Superionic Conductors (Ed. M.B. Salamon ), Springer-Verlag, New York, 1979, p. 77.
T. Geisel, in Physics of Superionic Conductors (Ed. M.B. Salamon ), Springer-Verlag, New York, 1979, p. 201.
R. Zeyher, in Fast Ion Transport in Solids (Eds. P. Vashishta, J.N. Mundy and G.K. Shenoy ), Elsevier North-Holland, 1979, p. 509.
L. Pietronero, S. Strassler and H.R. Zeller, in Fast Ion Transport in Solids (Eds. P. Vashishta, J.N. Mundy and G.K. Shenoy ), Elsevier North-Holland, New York, 1979, p. 159.
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Rahman, A., Vashishta, P. (1983). Molecular Dynamics Studies of Superionic Conductors. In: Perram, J.W. (eds) The Physics of Superionic Conductors and Electrode Materials. NATO Advanced Science Institutes Series, vol 92. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-4490-2_7
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