Journal of the Korean Physical Society, Vol. 38, No. 4, April 2001, pp.

377383

Lattice Mechanical Properties of Pd, Pt and Ni - A Model Potential Approach

C. V. Pandya, P. R. Vyas, T. C. Pandya, N. Rani and V. B. Gohel
Department of Physics, School of Sciences, Gujarat University, Ahmedabad 380 009, India (Received 22 August 2000) A Model potential, which has been found to be extremely useful in predicting liquid state properties of transition metals, has been examined, for the rst time, for its ability to reproduce the solid- state properties of Pd, Pt, and Ni. It is found that this model is better than all previously proposed models, and the results obtained are better than those obtained with more sophisticated models. The present study conrms the recent observation that pseudopotential techniques may now be used for transition metals.

I. INTRODUCTION Over the past 40 years, phonon spectra of crystals have been determined by using neutron scattering experiments for a wide class of systems ranging from elements to multicomponent materials, metals to semiconductors, insulators and alloys [1,2]. With the increasing computational power of modern work stations ab initio calculations of phonons have become possible. These investigations all based on a density functional theory [3,4] dier, however, in the treatment of the tightly bound core electrons and/or in the basis set used for describing the wave functions. Since very accurate full- potential calculations [e.g., full-potential linearized augmented-plane wave(FLAPW)calculations]are very time consuming, even with modern work stations, most studies have been restricted to selected phonon modes by using the frozen phonon approach [5]. Calculations of the entire phonon spectrum have been carried out in the past mostly by using generalized response theory [6,7]. Baroni and co-workers, as well as other groups, have used the formalism within a plane-wave basis and with pseudopotentials [810]. Linearized-MunTin-Orbital (LMTO)versions [11,12] and FLAPW versions [13] have also been developed. See Ref. 14. A number of attempts have been made to investigate the lattice properties of transition metals in a simplied way [15,16]. A widely used approach based on a concept of quasilocalized d states on the background of a nearly uniform electron gas leads to dierent shell models. These models discussed in Ref. 17 usually contain free parameters determined by tting to experimental phonon spectrum. Thus, such an approach is insuPermanent address: Maitrai College, Delhi University, New Delhi, India. -377

cient in predicting the lattice dynamics and is not applicable in studies of static lattice properties. A more elaborated approach is due to the pseudopotential theory [18]. Even transition elements may be described by a local pseudopotential, provided that the valence is chosen appropriately [19,20]. It has been shown that secondorder perturbation theory with a local model AnimaluHeine-Abarenkov [21] pseudopotential gives a reasonable description of many lattice properties in the case of fcc transition metals [15,16]. Very recently, Eichler et al. [14] have shown that pseudopotential techniques may now be used to predict the lattice dynamics of transition metals. These authors found that dierent types of pseudopotentials could do the job. Katsnelson et al. [22] used a simple pseudopotential which allowed the determination of the phonon spectra and the temperature dependence of the lattice heat capacites of the transition metals as dicult as Ir and Rh. Greenberg et al. [23] and Ivanov et al. [24] succeeded in constructing a pseudopotential model for pair forces, which describes surprisingly well the transition metals. Nevertheless, for transition metals, it has become necessary to introduce some sophistication in order to obtain satisfactory agreement with experimental phonon frequencies [23]. It should be noted that the Kohn anomalies were previously obtained [25] for Pd and Pt in reasonable agreement by using a special potential and dielectric function, but the phonon frequencies of the corresponding T1 [110] branch were considerably underestimated. In more rigorous approaches, the calculated phonon spectra did not contain the anomaly in this branch [2632]. For transition metals, unlike what happens for simple metals, there is not a large number of suitable pseudopontentials. One of the most popular is that based on the rst-principles study made by Wills and Harrison

-378-

Journal of the Korean Physical Society, Vol. 38, No. 4, April 2001

Fig. 1. Phonon dispersion curves of nickel. Experimental points are from Ref. 41. The pseudopotential parameter, a = 0.25 a.u.

Fig. 2. Phonon dispersion curves of palladium. Experimental points are from Ref. 42. The pseudopotential parameter, a = 0.44 a.u.

[33] which uses separate treatments for the s-p and the d states, leading to an eective pair potential that takes into account the eect of s-d hybridization. Phonon dispersion curves obtained from this potential do not show any anomaly in the T1 [110] branch [34]. Essentially, for transition metals, one has to consider the fact that the tightly bound d-electrons hybridize with the nearly free electrons, resulting in a partially lled dband, crossing the Fermi energy. The presence of the d band has been a serious impediment to the application of pseudopotential perturbation theory for such systems. Bretonnet and Deroiche [35] have developed a pseudopotential which treats the s-p states by using an Aschrofttype empty core pseudopotential characterized by a core radius Rc and have made a suitable adjustment to incorporate the s-d mixing by using an approximate potential inside the core. The relative success of the model has been established from its application to liquid- state properties [3638]. On the basis of these successful applications of this model potential to liquid- state properties, we feel that it would be worth while looking at its adequacy in yielding the solid- state properties. Comprehensive unied studies of several metals with pseudopotentials are surprisingly rare [39]. Therefore, in this paper, we have chosen to study the phonon dispersion curves, the density of phonon states, max , <>, < 2 >, the variation of the Debye temperature with temperature, the mode Gruneisen parameter, and the elastic constants of Ni, Pd, and Pt.

The pseudopotential to be used is constructed from the superposition of two potentials, one to account for the s-p contribution and the other for the d-band contribution [35]. Taken together, these result in the following expression for the potential:
2

Vion (r) =
n=1

Bn e(r/na) r > Rc .

r < Rc (1)

= ZS /r In q-space, Vion (q ) = 4a3

8B 2 H 2 B 1 H1 + (1 + a2 q 2 )2 (1 + 4a2 q 2 )2 4Zs cos qRc . q2

(2)

The continuity of the potential and its rst derivative at r = Rc give B1 = B2 = Zs Rc [1 2a/Rc ] exp( ), Rc a 2Zs Rc [a/Rc 1] exp( ). Rc 2a (3) (4)

With Xn = n2 a2 q 2 and Yn = Rc /na, Hn is given by Hn = 2 exp(Yn )[Yn (1 + Xn) (1 Xn)] sin qRc naq + [2 + Yn (1 + Xn )] cos(qRc )]. (5)

II. THEORY
1. Pseudopotential

The parameter a is a measure of the softness of the repulsive potential. Zs is the number of s electrons. In the present calculations we have screened the above pseudopotential with the help of the Lindhard dielectric function corrected for the local eld factor due to Taylor [40]. The potential parameter Rc was calculated from Rc = 0.51Ra Zs
1 3

(6)

Lattice Mechanical Properties of Pd, Pt and Ni - A Model Potential Approach C. V. Pandya et al.

-379-

Fig. 3. Phonon dispersion curves of platinum. Experimental points are from Ref. 43. The pseudopotential parameter, a = 0.52 a.u.

Fig. 5. Phonon density of states (phonon frequency distribution) curves for palladium. The continuous line represents present results, and the dashed line represents experimental data [42].

3. Debye Temperature

The parameter a was adjusted to get an overall good t to the experimental phonon dispersion curves. The values of the parameters are noted in Figs. 1 3 for Ni, Pd, and Pt, respectively.In all the cases, we have taken Zs = 2.

The frequency distribution curves generated using a standard technique [44] were used to compute the temperature variation of the Debye temperature. The relevant expressions are well known and may be found in Ref. 44.

2. Phonon Dispersion Curves

4. Elastic Constants

The phonon dispersion curves, Figs. 1 3, in the major symmetry directions were obtained by diagonalizing the dynamical matrix. The expressions for the matrix elements were taken from Wallace [44].

The elastic constants C11 ,C12 ,and C44 were calculated by the method of homogeneous deformation. In the present study, we used the expressions given by Wallace [44].

Fig. 4. Phonon density of states (phonon frequency distribution) curves for nickel. The continuous line represents present results, and the dashed line represents experimental data [41].

Fig. 6. Phonon density of states (phonon frequency distribution) curves for platinum. The continuous line represents present results, and the dashed line represents experimenall data [43].

-380-

Journal of the Korean Physical Society, Vol. 38, No. 4, April 2001

Fig. 7. Debye temperature as a function of temperature for nickel. Experimental points are from Ref. 46.

Fig. 9. Debye temperature as a function of temperature for platinum. Experimental points are from Ref. 47.

5. Mode Gruneisen Parameters

The mode Gruneisen parameter, (q, j ), describes the change in the frequency (q, j ) of the phonon of wave vector q, and the branch index j with volume and is dened by (q, j ) = d[ln (q, j )]/d[ln ] (7)

(q, j )s were calculated by computing (q, j )s at normal volume and at 10 % compressed volume, respectively, and using eq. [7] as a nite dierence equation.

III. RESULTS AND DISCUSSION

1. Phonon Dispersion Curves

The calculated phonon dispersion curves in the major symmetry directions for Ni, Pd, and Pt are shown in Figs. 1 3 along with the experimental ones [4143], respectively. The overall quantitative agreement is very good. The maximum deviation is about 10 % only at certain modes of vibrations. Unlike some previous calculations, the transverse branches are not underestimated. More remarkable is the reproduction of the anomalous features of the phonon dispersion in the transverse T1 [110] direction for these metals. It is interesting to see that the model potential predicts the phonon anomaly in platinum at q = 0.25. Experimentally, this anomaly is found at q = 0.33. In the case of palladium, the anomaly is found (although less pronounced as compared to that found in Pt) at q = 0.25. The anomaly almost disappears in Ni. The same behavior is observed in experimental results. The presently obtained results are better than those obtained by Antonov et al. [15] as far as overall agree-

Table 1. Maximum phonon frequency max , mean frequency < >, and < 2 > for Ni, Pd, and Pt (All in THZ). Present Exp. Antonov et al.[15] Present Exp. Antonov et al.[15] present Exp. Antonov et al.[15] Ni 56.52 55.79 [49] 52.15 34.01 37.94 [49] 37.83 28.04 35.95 [49] 36.45 Pd 43.96 44.09 [42] 45.46 26.15 28.39 [42] 28.64 20.56 26.49 [42] 26.45 Pt 38.93 36.74 [43] 37.56 21.77 23.39 [43] 23.97 17.27 21.90 [43] 22.64

max

<>

< 2 > Fig. 8. Debye temperature as a function of temperature for palladium. Experimental points are from Ref. 42.

Lattice Mechanical Properties of Pd, Pt and Ni - A Model Potential Approach C. V. Pandya et al.

-381-

Fig. 10. Mode Gruneisen parameter dispersion for nickel.

Fig. 12. Mode Gruneisen parameter dispersion for platinum.

ment with experiments is concerned. It should be noted that in the model calculations of Antonov et al., the dband eects were accounted for with the help of a twoparameter empirical Born-Mayer- type interatomic potential. Thus, their model contains four parameters. In the present work, we have only one adjustable parameter.Also,we have not considered the Zs as an adjustable parameter. Our results for Pd are also better than those due to Singh [34]. It may be noted that in the work by Singh, the phonon anomaly was not obtained. Our results are also better than those recently reported by Guevara et al. [45], who used the model potential based on the tight- binding approach.

The Debye temperature, D , is perhaps the most sensitive property for testing the validity of any lattice dynamical model. To compute the D -T relation, one must calculate the phonon density of states distribution. The calculated phonon density of states for Ni, Pd, and Pt are shown in Figs. 4 to 6, respectively. These curves show good agreement with those obtained from a BVK (Born Von Karmann) t to the inelastic neutron scattering data for Ni [41], Pd [42], and Pt [43]. In Figs. 7 to 9 we represent our calculated D -T curves, along with the experimental points for Ni [46], Pd [42] and Pt [47]. Again, the agreement between experiment and theory is fairly good.

2. Debye Temperature

Table 2. Elastic constants (C11 , C12 , and C44 ) and Bulk moduli for Ni, Pd, and Pt (All in M bar). Present Exp. [51] Antonov et al. [15] Present Exp.[51] Antonov et al. [15] Present Exp. [51] Antonov et al. [15] Present Exp. [51] Antonov et al. [15] Ni 2.610 2.465 1.703 1.261 1.473 0.557 1.221 1.247 1.343 1.710 1.804 0.939 Pd 2.311 2.314 1.568 1.168 1.760 1.134 0.982 0.712 0.968 1.55 1.95 1.27 Pt 3.70 3.47 2.74 1.70 2.51 1.85 1.17 0.765 0.852 2.37 2.83 2.15

C11

C12

C44

B Fig. 11. Mode Gruneisen parameter dispersion for palladium.

-3823. max , < > and < 2 >

Journal of the Korean Physical Society, Vol. 38, No. 4, April 2001

The quantities max , < > and < 2 > represent the main numerical characteristics of the density of phonon states. The presently calculated values of max , < > and < 2 > are compared with experimental values [42,43,48] in Table 1. In the same table, we also give the theoretical values due to Antonov et al. [15]. It can be seen from Table 1 that the values obtained in the present study agree very well with experimental ones and also with the theoretical values due to Antonov et al., who used a four- parameter lattice dynamical model. The present model contains only one parameter.

any experimental elastic constant to t the model parameter. It is in this context that the agreement of the present theoretical results with experiment, which in some cases is better than that achieved by Antonov et al., should be regarded as speaking in favor of the present model.

IV. CONCLUSIONS We have successfully used a comparatively simple local model potential for the transition metals. This conrms the earlier observations that for transition metals, an efcient use of a local model pseudopotential is possible. Our model, unlike the previously reported models, contains only one adjustable parameter. The present model is found to be fairly satisfactory, even without adjustment of the valence. The model does not need any additional empirical term to account for d- band eects. The present model does not contain any empirical, corecore repulsion in the interatomic potential. With the simplicity of the model, the calculations are not time consuming and, therefore, may be exploited for theoretical investigation of a large number of lattice mechanical properties. REFERENCES
[1] H. Bilz and W. Kress, Phonon Dispersion Relations in Insulators (Springer, Berlin, 1979). [2] Zahlenwerte und Funktionens Naturwissenschaft und Technik, Landolt-Bornstein, New Series, III, 13a (Springer, Berlin, 1981). [3] P. Hohenberg and W. Kohn, Phys. Rev. B 136, 864 (1964); W. Kohn and L. J. Sham, Phys. Rev. A 140 1133 (1965); W. Kohn in Highlights of Condensed Matter Theory , edited by M. P. Tosi, M. Fumi and F. Bassani (North-Holland, Amsterdam, 1985). [4] R. O. Jones and O. Gunnarsson Rev. Mod. Phys. 61, 689 (1989). [5] K. Kune, in Electronic Structure, Dynamics and Quantum Structural Properties of Condensed Matter , edited by J. T. Devreese and P van Camp (Plenum, New York, 1985). [6] S. Baroni, P. Giannozzi and A. Testa, Phys. Rev. Lett. 58, 1861 (1987). [7] R. D. King and R. J. Needs, J. Phys. Condens. Matter 2, 3431 (1990). [8] P. Giannozzi, S. de Gironcoli, P. Pavone and S. Baroni Phys. Rev. B 43, 7231 (1991). [9] P. Pavone, K. Karch, O. Schutt, W. Windl, D. Strauch, P. Ginnozzi and S. Baroni, Phys. Rev. B 48, 3156 (1993). [10] C. Bungaro, S. de Gironcoli and S. Baroni, Phys. Rev. Lett. 77, 2491 (1996). [11] S. Y. Savrasov, Phys. Rev. Lett. 69, 2819 (1992). [12] S. Y. Savrasov, D. Y. Savrasov and O. K. Andersen, Phys. Rev. Lett. 72, 372 (1994). [13] R. Yu and H. Krakauer, Phys. Rev. B 49, 4467 (1994); Phys. Rev. Lett. 74, 4067 (1995).

4. Mode Gruneisen Parameter

Figures 10 to 12 display the mode Gruneisen parameters as calculated presently in the high-symmetry directions. To the best of our knowledge, the mode Gruneisen parameters of Ni, Pd and Pt have not been measured. The experimental data, based on tunneting spectroscopy, indicate that the Gruneisen parameter is necessarily mode dependent and that the transverse modes are more sensitive to compression than the longitudinal ones. A recent calculation of these parameters is due to Antonov et al. [16]. Our values are much smaller than those reported by Antonov et al. This is not surprising for two reasons. First, we have calculated the q s at 0 K. It is well known that as temperature decreases, decreases rapidly in the temperature range below 20 K. See for example, Ref. 48. Secondly, in our model calculations, we have not used any empirical, corecore repulsive potential. Introduction of such a potential makes the interatomic potential much steeper at smaller atomic separations. This results in a large compression of the phonon frequency. We believe that it is this repulsive Born-Mayer- type term in the work of Antonov et al. that is responsible for the comparatively large values of the mode Gruneisen parameters. It seems that a Born-Mayer type of repulsive interaction term in the interatomic interaction is necessary to account for the pressure- dependent properties. The importance of such a term, even in liquid metals, has been emphasized by Gonzalezmirranda and Torra [50].

5. Elastic Constants

The presently obtained values of elastic constants, C11 , C12 , and C44 , are given in Table 2. We have compared our values with the experimental ones and also with those computed by Antonov et al. [15]. It should be noted that Antonov et al. determined their model parameters by a least- squares t with experimental elastic constants. In the present work, we have not used

Lattice Mechanical Properties of Pd, Pt and Ni - A Model Potential Approach C. V. Pandya et al. [14] A. Eichler, K. P. Bohnen, W. Reichardt and J. Hafner, Phys. Rev. B 57, 324 (1998). [15] V. N. Antonov, V. Yu Milman, V. V. Nemoshkalenko and A. V. Zhalko Titarenko, Z Phys. B-Condensed Matter 79, 223 (1990). [16] V. N. Antonov, V. Yu Milman, V. V. Nemoshkalenko and A. V. Zhalko Titarenko, Z Phys. B-Condensed Matter 79, 232 (1990). [17] S. K. Sinha in Dynamical Properties of Solids, edited by G. K. Horton and A. A. Maradudin (North-Holland, Amsterdam (1980). [18] E. G. Brovman and Yu M. Kagan in Dynamical Properties of Solids, edited by G. K. Horton and A. A. Maradudin (North-Holland, Amsterdam, 1974) 1, p. 191. [19] T. Starklo and J. D. Joannopoulos Phys. Rev. B 16, 5212 (1977). [20] D. Vanderbilt and J. D. Joannopoulos, Phys. Rev. B 27, 6296 (1983). [21] I. V. Abarenkov and V. Heine, Phil. Mag. 12, 529 (1965); A. O. E. Animalu and V. Heine, Phil. Mag. 12, 1249 (1965). [22] M. I. Katsnelson, I. I. Naumov, A. V. Trelov, M. N. Khlopkin and K. Yu Khromov, Phil. Mag. B 75, 389 (1997). [23] B. A. Greenberg, M. I. Katsnelson, V. G. Koreshkov, Yu N. Osetskii, G. V. Peschanskikh, A. V. Frelov, Yu F. Shamanacv and L. I. Yakovenkova, Phys. Stat. Sol. (b)158, 441 (1990). [24] A. S. Ivanov, M. I. Katsnelson, A. G. Mikhin, Yu N. Osetskii, A. Yu Rumyantsev, A. V. Trelov, Yu F. Shamanaev and L. I. Yakovenkova, Phil. Mag. B 69, 1183 (1994). [25] S. C. Vrati, N. Rani, D. K. Gupta and H. C. Gupta, Phys. Lett. 79A, 342 (1980). [26] N. Singh, N. S. Banger and S. P. Singh, Phys. Rev. B 38, 7415 (1988). [27] A. O. E. Animalu, Phys. Rev. B 8, 3555 (1973). [28] O. P. Kulshrestha and J. C. Upadhyaya, Phys. Rev. B 13, 1861 (1976). [29] D. Prakash and J. C. Upadhyaya, J. Phys. Chem. Solids 49, 91 (1988).

-383-

[30] B. B. Tripathi and S. Nand, Phys. Lett. 70A, 241 (1979). [31] W. Weber in Electronic Structure of Complex Systems, edited by P.Pharisean and W.M.Temmermann (Plenum, New York, (1984), p. 345. [32] M. S. Daw and M. I. Backes, Phys. Rev. B 29, 6443 (1984). [33] J. M. Wills and W. A. Harrison, Phys. Rev. B 28, 4363 (1983). [34] N. Singh, Physica B 269, 211 (1999). [35] J. L. Bretonnet and A. Deroiche, Phys. Chem. Liq. 24, 169 (1991). [36] J. L. Bretonnet, G. M. Bhuiyan and M. Silbert J. Phys. Condens. Matter 4, 5359 (1992). [37] G. M. Bhuiyan, J. L. Bretonnet, L. E. Gonzales and M. Silbert, J. Phys. Condens. Matter 4, 7651 (1992). [38] O. Akinlade, A. M. Ummar and L. A. Hussain Pramana, J. Phys. 47, 271 (1996). [39] L. Pollack, J. P. Perdew and J. He, Phys. Rev. B 55, 15544 (1997). [40] R. J. Taylor, J. Phys. F 8, 1699 (1978). [41] R. J. Brigeneau, J. Cordes, G. Dollings and A. D. B. Woods, Phys. Rev. 136, 1359 (1964). [42] A. P. Miller and B. N. Brockhouse, Can. J. Phys. 49, 704 (1971). [43] D. H. Dutton, B. N. Brockhouse and A. P. Miller, Can. J. Phys. 50, 2915 (1972). [44] D. C. Wallace, Thermodynamics of Crystals (Wiley, New York, 1972). [45] J. Guevara, A. M. Llois and M. Weissmann, Phys. Rev. B 52, 11509 (1995). [46] P. K. George and E. D. Thomson, J. Phys. Chem. Solids 28, 2539 (1967). [47] W. T. Berg, J. Phys. Chem. Solids 30, 69 (1969). [48] A. C. Buley, N. Waterhouse and B. Yates, J. Phys. C 2, 769 (1969). [49] B. I. Gorbachev, P. G. Ivanitskii, V. T. Krotenko and N. V. Pasechnik, Ukr. J. Phys. 18, 558 (1973). [50] J. M. Gonzalezmiranda and V. Torra, Phys. Lett. A 103, 126 (1984). [51] C. Kittel, Introduction to Solid-State Physics (Wiley, New York, 1997).