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REVIE%'
of state of metals
James H. Rose
U
Ames Laboratory
S. Department of Energy, * Iowa State University, Ames, Iowa 50011
and Institute for Theoretical Physics, University of California, Santa Barbara, California 93I06
John R. Smith
Institute for Theoretical Physics, University of California, Santa Barbara, California, 93106
and Physics Department, * Genera/ Motors Research Laboratory, Warren, Michigan 48090-9055
Flanclsco GU1ncR
Institute for Theoretical Physics, University
California 93106
John Ferrante
Xationa/ Aeronautics and Space Administration, Lewis Research Center, Cleveland, Ohio 44135
(Received 29 June 1983)
The zero-temperature equation of state of metals, in the absence of phase transitions, is shown to
be accurately predicted from zero-pressure data. Upon appropriate scaling of experimental
pressure-volume data a simple universal relation is found. These results provide further experimental confirmation of the recent observation that the total-binding-energy
versus
separation relations for metals obey a universal scaling relation. Important to our results is a parameter q, which
is a measure of the anharmonicity of a crystal. This parameter is shown to be essential in predicting
the equation of state. A simple formula is given which predicts the zero-temperature derivative of
the bulk modulus with respect to pressure.
I. INTRODUCTION
Many aspects of the energetics of metals can be understood if the zero-temperature equation of state (EOS) is
known. Predictions of the EOS are difficult and therefore
rare. In this paper we will show that the zero-temperature
EOS of metals (both alloys and elements) can rather generally be determined, in the absence of phase transitions,
from a universal function. These results also allow the approximate determination of the pressure-volume relation
for the experimentally inaccessible regime of negative hydlostRtlc pI'cssurc Rs well as thc ultfa41gh"pI'cssUrc 1"cglIIlc.
Recently, three of the authors' ' have examined the nature of metallic bonding. It was predicted on the basis of
theoretical calculations that the binding-energy
distance
relation could be quantitatively
described in terms of a
simple two-parameter scaling of a universal function and
knowledge of the equilibrium specific volume per atom.
The zero-temperature
EOS follows directly from the
universal energy relation and is specified by the zero pressure, equilibrium values of the cohesive energy b, E, the
isothermal bulk modulus Band the specific volume per
atom, which we characterize by the Wigner-Seitz equilibr1UIIl fad1Us P'wsE.
F'~
1984
2964
29
II. THEORY
Detailed, first-principles calculations of the cohesive enof metals as a function of lattice parameter have ap' It has recently been shown'"'
peared in recent years.
that the shape of these curves can be obtained from a simple two-parameter scaling of a universal function E*(a'),
ergy
E(rws) = DE E'(~*)
U
CC
(2. 1)
04
LLI
Here
E is
res is the
radius
rwsE
)/I
(2.2)
-0.6
C5
e)
6)
LU
-0.8
The equilibrium
2.0
SCALED SEPARATION
6.0
a
FIG. 2. Binding
P(V)=
z
4~rws I
E* (a") .
(2.3)
0(
4.0
(2.4)
0. 1
-0.2
(9
-0.3
-0.4
0.5
~ -06
C3
llj
-0.7
0.8
-0.9
I
-1.0
FIG. l. Bulk
2
5
3
4
SCALED SEPARATION
-2
a*
F( V) =~F*(a"),
* (a').
=b,Eil and F*(a*)= E
where
(2.5)
Figure 3
shows the universal function F*(a'). Note that F* has a
m1nlmum at Q
l.
A second universal function, G*(a*), which may have
use in experimental data analysis, can be derived from Eq.
(2.5). We note that the force depends linearly on a' near
equilibrium. Thus, we can rewrite I'*=a*6*. Explicitly,
6* is given by
4m. r wsl2
6'(a')=
~E ( &ws &wsE )
P(V) .
(2.6)
"
(2.7)
1 2wBI'wsE
"
1/2
1 2%St"' wsE
(2.8)
AE
The length scale l describes the width of a bindingenergy curve. Consequently, it describes the distance over
which strong forces act when the crystal is uniformly dilated. In confirmation of this point of view, it has been
shown in Ref. 1 that I is given to fair accuracy by an ap-
-2.
TABLE I. Scaling length I [Eq. (2.7)], equilibrium Wigner-Seitz radius (Ref. 11), and dimensionless parameter, g =rwss//, which
describes the anharmonicity are given. For each element, first line gives value of I (in A), second line gives value of r~sE (in A), and
third line gives value of g.
Li
Be
. 553 . 312
1.719 1.25
3. 10
Na
. 562
2. 080
3.70
K
.651
.658
.714
Fr
Ne
Al
Si
Cl
Ar
As
Se
Br
Kr
Te
Xe
Po
At
Rn
1.58
4. 71 4. 88
5. 60
T1
Ca
Sr
Cr
Fe
.483
'4. 76 4. 81
5. 59
Zr
No
Nb
4. 23 4. 48 4. 84
,
Ba
. 558
La
6.04
5.85
Re
Os
4. 41
Ra
Ta
Hf
Co
Ni
CU
Ga
ZA
IIe34&
. 274 . 262 i 270 . 272 . 215
1.76
1.41 1.39 1.38 1 .41 1.54
5.05
5. 16 5. 31 5. 11 5. 20 7. 16
Rh
RU
Pd
Cd
In
Sn
Sb
. 245
. 237 Ag. 269 . 214 .360
1 . 48
1.52 1.60 1.73 1.84
2. 977 2. 46
4. 17
.336 0. 341
. 316
1.77
2. 750
4. 18
Cs
4. 01
Mg
2. 573 2. 18
3.94 4. 52
Rb
6. 41
Ir
Pt
. 230 . 237
1.50 1.53
6. 52 6. 47
5. 94
Au
. 236
8.08 5. 1t
Tl
Hg
Pb
. 331 . 303
1.90 1.93
. 59
6.75
Bi
5. 74 5. 37
Ac
Ce
Eu
2. 02
3. 11
Th
.483
1.99
4. 12
Gd
. 478 .467
2. 27 1.99
4. 75 4. 27
. 648
Pa
Np
Pu
Am
Cm
Tb
Dy
. 404
Ho
1.96
Cf
. 393
Tm
Es
Fm
Yb
. 506
Lu
1.99
1.94
3.94
4. 94
4. 85
Bk
Er
t))td
No
Lx
TABI.E II. Cohesive energy and the bulk modulus are tabulated for many metals (Refs. 11 and 12). In addition, the theoretical
limit for the characteristic negative hydrostatic pressure, I'g/8, at which a metal ruptures, is tabulated. For each element, first line
gives value of AE (eV), second line gives value of (10' dyn/cm ), and third line gives value of
Pz /9.
Li
1.65
Be
3.33
1.144
. 17
Na
Mg
1.13 1.53
.0729 . 369
Al
Si
Ne
Xe
133
. 21
3. 34 4. 64
.794 0. 99
.15
. 19
14
Ca
.941 1.825
.0366 (.152
. 18 ..16
~
Ti
Rb
.858
.0306
1.097 1.570
.15 . 15
Y
Zr
Nb
4. 39 6. 32 7. 47
.
.423 973 1.730
Sr
.17
Cs
. 17
Ba
. 17
. 15
.15
Ta
Hf
La
.827 1.86
.0231 (.103
Fr
Cr
4. 86 5. 30 4. 10
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Tc
Ru
Rh
P&I
Ag
Cd
In
Sn
Sb
Te
Re
Os
Pb
Bi
Po
4. 29 4. 39 4. 435 3. 50 1.35
1.724 1 .948 1.876 1.420 .804
. 14 . 14 . 15 . 14 . 11
1.901
. 14
Mo
6. 810
6.62
3. 152
. 13
2. 653
. 13
6. 35 8.089 8.66 8. 10
1.106 1.942 3. 142 3.715
. 16 . 15 . 13 . 13
. 16
3.87
0.77
3.936 2. 96 1.16 2. 6
1.955 1.087 .621 .464
. 12
. 13
Ir
Pt
Au
6. 93 5.852 3.78
3.704 2. 884 . 803
12
. 12 . 12
.14
. 10
Tl
Hg
1.87 2. 04
. 38'. 488
'I
. 12
Ac
Ra
Ce
Eu
(.. 239)
21
(.. 147I
Th
Gd
1.80 4. 14
4. 77
15
Pa
Np
Pu
Am
Tb
Dy
Ho
Er
Tm
Yb
Bk
Cf
Es
Fm
Md
No
3. 1
. 411
. 15
. 405
. 17
Cm
3. 3
. 468
. 15
1.6
(. 133)
~
Lu
17
5. 926
(.543)
. 17
8.
EO(a4)
where
f4(a4)e 8
(2.9)
f* can be represented
a' ~ 1). We assume that
(2. 10)
The constraints introduced by E*(0)= 1, E" (0) =0, and
E* (0)=1 require that f', = 1, f', = 1, and
f', =0.
)'"1
(viv, )'"
3 (VyV,
'
0. 15a*+0.05a*
(1
(2.11)
Here Vo
4mrwsE/3.
Two quantities
teristic of the pressure can be extracted from this equation. The bulk modulus is characteristic of the behavior
near the minimum.
The second characteristic pressure
corresponds to a theoretical limit on the negatiue hydrostatic pressure at which a solid ruptures. This pressure,
P~, corresponds to the minimum in Eq. (2. 11). Typically,
20% of the bulk modulus. As a fraction of the
Pz is 10
bulk modulus, I'~ is largest for the more harmonic solids
(7) small) and smallest for the anharmonic solids. Values
of PR for many elemental metals are included in Table II.
The description given above allows the derivative of the
bulk modulus with pressure to be determined, starting
from the definition
8= V
I'
(2. 12)
BV
BB
dP
=i- "wss
3l
E* (0)
E*"(0)
E* (0) and E*
(2. 13)
c}P T
2. 3
~wsE
(2. 14)
A similar although more tedious derivation can straightforwardly be carried through for (d 8/dP')T and higherol der deIlvatlves.
on the compression of metals with pressure [V(P)] and use them to test
our hypothesis of a universal form for E'{a*)and F'{a*).
Two types of experiment were considered. First, there are
static press mcasurcIDcnts which wcIc IDadc by Brldgman
'" The second class of experiments involve
up to 100 kbar.
shock-wave experiments'
in which metals are collided at
'
high velocities. Very large compressions ( V/Vo- , ) and
pressures (up to 10 Mbar) have been achieved by this technique. Unfortunately, the determination of both the pressure and volun1e are indirect. For example, in a shockwave experiment on Pd, the internal temperature is as
high as 7000 K. From a model of the shock-wave experiment, thc cxpcrinlcntalist predicts R zero-temperature 1sotherm. Clearly, some room for systematic error lies here.
Mao et al. ' have used shock-wave data' for four elements (Pd, Ag, Cu, and Mo) to estabhsh a high-pressure
scale based on a ruby crystal fluorescence line. Given the
importance of this scale, we have included these four eleIDents in our studies. Agreement between theory and experiment not only tests the hypothesis, but also tests the
accuracy of the shock-wave data and analysis.
In Fig. 4 we show the experimental EOS's for four metals and compare therD with the theory. Similarly, Fig. 5
shows the same comparison for four other metals. Note
particularly that an alloy [stainless steel 347 (Ref. 18), taken as 70% Fe, 19% Cr, and 11% Ni for our calculations]
has been included. The data for Li and Rb come from
Bridgman's work'" and thus are independent
of the
shocked-wave analysis. The theory curves use Eq. (2. 11)
and the zero-pressure data rn Tables I and II. The elemental input data have been taken from handbook values extrapolated to zero temperature and have not been adjusted
to improve agreement. In the case of stainless steel the
bulk modulus was determined from the experimental data
and l was found by an average over the concentration for
the constituent elements. As can be seen, the overall
agreement for the eight metals plotted is good. For five of
the cases (Li, Rb, Ag, Cu, and stainless steel) the agreeIDent is essentially exact. For Pd, Mo, and Pt the small
discrepancy ls UncxplMncd. Its orIgln may llc either In R
small correction to our hypothesis or more probably in the
analysis of the shock-wave data. Overall the agreement
between theory and experiment is satisfactory.
The clearest demonstration of a universal relation results from scaling the experimental data using the zeropressure data rwsE, b, E, and B. As discussed in Sec. II the
function F*(a*) is expected to have a universal form. F*
can be related to experimental results via Eqs. (2.4) and
(2.5), which yield
1
rwsE
vo
P(V)
Stainless
Steel
C,
2.0
0.5
CL
CL
Oc
1.0
Ot.
1.0
0.6
I
CU
Li
& 0,5
"
Theory
Experiment
Oc
1.0
0.8
Ot.
1.0
OA
0.8
V/Vo
0.6
V/Vo
FIG. 4. Predicted
E'(a')
I"
to approximately
F*(a*)=a'e
{3.2)
Theory
ExperlfTlent
Z)
6.0
& 0.5
4.0
0
1,0
0(.
0.6
1.0
OA
1.0
Pd
Mo
(3. 1)
Og
1.0
0.8
0.6
0.4
V/Vo
Og
1.0
0.8
0.6
OA
V/Vo
Ag
Cu
Stainless Steel
0.5
IV. DISCUSSION
Li
Rb
pt
pd
Mo
0+
0.3
0.7
0.5
Q
0.9
4'
TABLE III. (88/BP)z 0 is predicted for many of the elemental metals and compared with experiment when it is available. Experimental results for Na, K, Rb, and Cs are from Ref. 20; Li from Ref. 21; Al from Ref. 19; Cu, Ag, and Au from Refs. 22 and 23;
Si and Ge from Ref 9; Nb, Mo, Ta, and % from Ref. 24; Pb from Ref. 25; and Fe from Ref. 26. For each element, the first line gives
the value of BB/BT r 0 from theory, and the second line gives the value from experiment.
~
Li
Be
Ne
Na
Mg
A1
Si
Cl
Ar
Ca
Sc
Ti
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Br
Kr
Rb
Sr
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Te
Ba
La
Hf
Ta
Re
Qs
Ir
Pt
Au
Hg
T1
Pb
Bi
Po
At
Ho
Er
3. 38
3. 5
4. 07
3.84 5. 29
3.90
4. 02 6. 28
4. 07
4. 20
4. 07
Cs
4. 20 4. 38
4. 61 4. 74
4. 72 4. 2
4. 43 4. 72
4. 1
3.98
Fr
Ra
4. 65 4. 69
4. 5? 4. 77
3.8
5. 29
5. 49
4. 7
4. 96 5.07 4. 92
5. 29
5. 63
5. 36 5. 72
4. 5
4. 99 6. 49
5. 25,
5. 91 5. 55
5.87
600 596
618
7. 19 4. 92
4. 84
4. 6
5. 40 5.88
5. 45
5. 90
Rn
Ac
Sm
Eu
4. 64
NP
Pu
Am
Gd
Tb
Dy
4. 72
4. 27
Cm
Bk
Tm
Yb
Lu
Md
No
Llsl
4. 79
Es
Fm
29
of E*, i.e.,
F'(a')=
" (a*).
2969
'Permanent
and 3835.
A. Morgan, High Temp. High Pressures 6, 195 (1974), and
references therein.
H. K. Mao, P. M. Bell, J. W. Shaver, and D. J. Steinberg, J.
Appl. Phys. 49, 3276 (1978).
'7W. J. Carter, S. P. Marsh, J. N. Fritz, and R. G. McQueen,
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I J. A. Morgan, High Temp.
High Pressures 7, 65 (1975).
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M. S. Anderson and C. A. Swenson, Phys. Rev. B 28, 5393
(1983); the tentative value for Cs is due to M. S. Anderson and
C. A. Swenson (unpublished).
R. A. Felice, J. Trivisonno, and D. E. Scheule, Phys. Rev. B
address.
(1982).
J. Ferrante, J. R. Smith,
J. H.
Proceedings
Conference,
(1983).
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1385 (1983).
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Papers (Harvard
University Press, Cambridge, Mass. , 1964), Vol. 6, pp. 3819
ACKNOWLEDGMENTS
~5J.
(1969).
M. W. Guinan and D. N. Beshers, J. Phys. Chem. Solids 29,
541 (1968).
27For example, G. Schattner, and A. Bloch, in Structure and
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2