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    187 coordinate &;). ‘The modes of intermediate frequency are therefore correspondingly closely related to Ss, as Spitzer etal, have suggested. On the other hand, the mode pattern for the fuoride seems qualitatively different. Although the difference Detween the alternative solutions is greater here, at least one of the solutions for the low-frequency mode is very similar to S: as Last originally proposed forthe oxides, and as would be expected if the negative fons were strongly coupled to the B sublattice and very loosely coupled to the 4 sublattice. One is tempted to argue that this is indeed the normal state of affairs in perovskite lattice with anions less polarizable than ‘oxygen and thus unable to supply the favorable long- range B—Xy, coupling necessary to stabilize the Slater” mode ince the eigenvalues of the dynamical matrix are known experimentally, once the eigenvectors are fixed, the machinery of matrix diagonalization can be re- versed to obtain the various sublattice coupling con- VIBRATIONAL EIGENMODES OF BaTiOy 435 stants. Because of the two-fold ambiguity arising from envector choice, only general features charac- of all of the solutions studied are worthy of comment. First of all, the strongest sublattice coupling im all cases is between the anions, This is of course a direct consequence of the assumption concerning the form of the high-frequency modes, but an argument for its physical plausibility has been made as well. The second feature common to all solutions is the small magnitude of the net B—X coupling constants. In fact for BaTiOs, SrTiOs, and one of the two KTaOs solutions, the coupling constants are found to be at- tractive (ie, a displacement of X toward B results in a force on B directed towards X). It is of course obvious that this situation favors the ferroelectric transition. This situation can be understood to come about in large measure from the abnormal long-range force con- stants calculated in Sec. If, which in turn have their gin in the high-local electric fields existing along the B=X;, axis, just as Slater visualized. Infrared Dielectric Dispersion of Several Fluoride Perovskites J.D. Axz ano G.D. Peeerr BME Wotson Research Center, Vorkiown Height, New York (Received 2 Deceer 1966) ‘Measurements at room temperature of the infrared relectivity, frequency dielectri constant (4), and optical index of refraction (a) have been made on KCoF,, Kn and RMoF The reflectivity data have een analyzed using Keamers-Kronig relations to obtain the dielectric digpesion from 30 em to 4000 cm. The frequencies of the thre transverse opte (longitudinal optic) long-wavelength pola iges- modes are 139 (168), 225 KMar, for KCof, KMnf, and RbMaF, (203), 417 (S00) em! for KCoPy; 115 (149), 198 (268), 395 (479) em for rnd 113 (128), 197 (273}, 360 (482) em for RDM spectively. Mfode strengths a damping were also measired. Low tem 358.28, 76 and w= 1.4, 14, 1.53 perature reflectivity measurements on antfertomagnetically ordered Ko, were also performed. I. INTRODUCTION IHE. study of the lattice dynamics of the cubic perovskite structure has proved quite fruitful Many, though by no means all, of the binary oxide perovskites are unstable and distort. spontaneously at low temperatures into ferrocletrcally or antiferro- dlectrcally ordered states! In their cubic phases these compounds have large low-frequency dielectric con- stants which arise predominantly from the response of the lowest frequency polar eigenmode of long wave- Jength* Compounds other than binary oxides havi the perovskite structure seem not to have anomalous Paraly supported by Army Reseazch Ofc, Durham, North cari, nde Cone Se BASSE ARES a” ferocecrice ee FP Jona and G. Shanes Force Cosas {enpon Pres, i, New York 162) Chap. V. WP Cocurany Advan, Piva 9387 C80)" 14°. Barker and Af, Tiabhah, Phys. Rev, 125, 1527 (196), {ANG Splogy Ry Ce iler’D.”A. Kisame and le 2 ovat, iy Rey. 126, 1710 (9) THEA! Covey, Pye Rev. 13, AGL (1964). diclectric properties, and it is interesting to inquire into the underlying causes for these differences. The alkali-transition metal fluorides. are. well suited for such a study. An additional incentive for studying these compounds is that they are known to undergo struc- tural changes accompanying magnetic ordering which must also ultimately be understood on the basis of lattice dynamical. considerations. IL, RESULTS Samples were cut and polished by standard metallo- graphic procedures, with a final polish on 0.05. alumina. All reflectivities were measured at room tem- perature and near normal incidence using point by point comparison with an aluminized surface in a Perkin-Elmer model 301 spectrometer. The frequency SS ach id Seaganan E Sacell, Po Rey. 138, A121 (i965) for additional experimental details Ta the proseht Work, no attempt Wat made to check for surace kage It was shown fo" be nepiibe im previous Aordes 436 yp 8s Flo. 1. The infrared reflectivity spectra of ROMP, and KMF, st rom temperstre, ‘The confindous curves were defined hy & lisge number of measurements at various ned frequencies throughout the range, The fdividdal date points ate not shows, range between 50 and 4000 em-t was covered with spectral slit widths between 1 and 6 em The results are shown in Figs. 1 and 2. Reflectivity measurements were repeated for KCoF, at liquid-nitrogen tem- peratures, ‘The optical constants were derived from the meas- ured reflectivity by use of the Kramers-Kronig relation between R(a), the fraction of reflected energy at a given frequency, and the phase shift (0), which occurs ‘upon reflection? 8(e)=(o/n) f (ew) InLR(W)/R(W) Mo!. (1) It is possible to deduce all of the optical constants of interest from R() and 0(.). Numerical integration of Eq, (1) and the subsequent calculations of the optical B83 8 a e'3 TF Stem, ia Sold Stole Physies (Academic Press Inc, New ‘York, 1963), Vol 15, pe 388. AXE AND G. D. PETTIT 0 of Fic. 3. The real part of the infrared ditectsic pe mee three binary” Guoride perovalites as derived. from ‘Kronig anal of the reetvty spect, constants were performed with the aid of an TBM 7094

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