PHYSICAL REVIEW B VOLUME 52, NUMBER 18 1 NOVEMBER 1995-II

Theoretical investigation of the high-pressure crystal structures of Ce and Th

Per Soderlind
Lawrence Livermore National Laboratory, University of California, P 0 B. o.x 808, Livermore, California 94550

Olle Eriksson and Borje Johansson

Condensed Matter Theory Group, Department of Physics, University of Uppsala, Box 530, S 751 21-Uppsala, Sweden

John M. Wills
Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
(Received 31 January 1995; revised manuscript received 22 June 1995)
The high-pressure crystal structures of Ce and Th are studied theoretically by means of a full potential linear
muffin-tin orbital technique, where the generalized gradient correction to density-functional theory has been
implemented. A crystallographic phase transition from fcc to bct is found for u-Ce at about 10 GPa, in good
agreement with experiment. The calculated pressure dependence of the crystallographic c/a ratio (of the bct
structure) is in good agreement with experiment. For n-Ce a subsequent transition to the hcp crystal structure
is predicted at about 1600 GPa. For Th a continuous transformation from fcc to bct at 45 GPa is found,
confirming recent experimental findings. Also for this material the calculated pressure dependence of the
crystallographic c/a ratio (of the bct structure) is in good agreement with experiment. For Th we also predict
a transformation to the hcp crystal structure at even higher pressures.

I. INTRODUCTION pressure-induced onset of a bct crystal structure in Th. Since

The metals Ce (Z= 58) and Th (Z= 90) are located at the
beginning of the 4f (lanthanides) and the Sf (actinides)
transition-metal series, respectively. Ce is the first lanthanide
metal that has an appreciable occupation of the 4f states, and
is a known subject for controversy. Primarily the debate con-
cerns the localized versus itinerant character of the 4f elec-
tron. The electronic structure of Ce has been reported
earlier. ' As regards the 5f population at ambient condi-
tions, calculations show that the actinide metal Th has a
smaller f occupation than ct Ce Se-ver. al recent investiga-
" note here that the experimental structure is not quite clear for
theoretical, '
tions of these two metals, both experimental as well as
have been motivated by their crystallographic
phase transitions under compression.
In the lanthanide series localized 4f states are progres-
sively being filled and their inhuence on the chemical bond-
ing is negligible. In the actinide series, however, the earlier
metals have delocalized 5f electrons that contribute to the
chemical bonding. The increasing 5f occupation as a func-
tion of atomic number results in increasingly distorted (com-
plex) crystal structures. This is understood from the in-
creased contribution to the bonding from the narrow 5f
bands. ' '" Particularly interesting in the present context is
the occurrence of the bct (c/a =0.825) structure at ambient
conditions for Pa (Z=91). The increased 5f occupation in
Pa, in comparison to Th, results in a bonding which favorizes
the bct crystal structure over the fcc structure (which is found
in Th at ambient pressure). The effect of pressure upon an
f
itinerant 5 metal is first a lowering of the energy of the 5f
bands relative to the other valence states and second a broad-
ening of the Sf band as well as a broadening of the other
bands. The relative lowering of the Sf states results in an
increased Sf population. Therefore, in view of the known
crystal structure of Pa (bct), it is not surprising to find a
u-Ce from certain aspects can be regarded as an analog ele-
ment to Th, a similar behavior (stabilization of the bct struc-
ture) of Ce under pressure is not surprising either. However,
for Ce, in contrast to Th, there is an intermediate body-
centered-monoclinic (bcm) phase found experimentally in
the interval 6 —12 GPa. This bcm structure can be seen as a
small distortion of the bct crystal structure, and can therefore
be, approximately, described as a bct structure. In fact both
the bcm and the bct phases of Ce at moderate compressions
can be viewed as more or less distorted fcc structures. We
Ce since it has been reported that an orthorhombic n-U type
of structure is stabilized, instead of the bcm structure. In the
present report we take the view point that the bcm and the
u-U structures are very close in energy and that the u-U
structure is probably metastable. For that reason we have
chosen to study the bcm rather the cv-U structure.
Recent experimental high-pressure work "
on u-Ce and
Th indeed seem to confirm the general picture outlined above
and this has encouraged us to theoretically investigate these
metals at ultrahigh compression. This has been done using
accurate calculations with a full potential linear muffin-tin
orbital (FP-LMTO) method for Ce and Th in the multi-
megabar range. Experimentally the observed structural
phase transition in n-Ce, i.e., fcc~ tx" (bcm)-phase — +bet, is
a sequence of two discontinuous, first-order phase transi-
tions. In Th a continuous phase transformation (along the
Bain deformation path), fcc~bct, has been measured" at
high pressure. The difference in the phase transition behavior
of Ce and Th metal (discontinuous versus continuous) is very
interesting, since an examination of the observed structural
data at high pressures for these two metals reveals remark-
able similarities. The high-pressure experiments which show
the above-mentioned differences and similarities for Ce and

0163-1829/95/52(18)/13 169(8)/$06. 00 13 169 1995 The American Physical Society

13 170 SODERLIND, ERIKSSON, JOHANSSON, AND WILLS
Th have further motivated us to undertake a thorough theo-
retical investigation of Ce and Th at high compression.
II. COMPUTATIONAL DETAILS
A full potential linear muffin-tin orbital method' is used
to calculate the electronic structure. The scalar relativistic
Pauli equation is solved with the spin-orbit coupling term
included in each variational step. ' In a full potential method
there are no geometrical constraints as regards the electron
density or potential. The present method divides the crystal
into nonoverlapping
functions are muffin-tin orbitals. ''
muffin-tin spheres, where the basis
For Ce the wave func-
tion is expanded in basis functions of 5s, 5p, 6s, 6p, 5d,
and 4f orbitals which are allowed to hybridize. For Th the
6s, 6p, 7s, 7p, 6d, and 5f orbitals are used. Two tail
functions with different kinetic energies (a ) are attached to
each basis function, i.e., a "double" basis is used with a total
of six different sc values. The radial part of these functions
outside the muffin-tin spheres is a solution to Helmholtz
equation, i.e., Neumann or Hankel functions (depending on
the sign of x ) whereas the angular part is a spherical har-
monic function. Inside the muffin-tin spheres a combination
of P, and P„(solution to the Schrodinger equation for a
spherical potential inside the muffin tins, @„and the first
energy derivative, @,) is used. In these calculations the muf-
fin tins are kept as large as possible (without overlapping one
another) which means that the muffin tins fill about 65% of
the total volume. The remaining 35% of the volume defines
the interstitial region in which the basis functions are repre-
sented in a Fourier series.
The sampling of the k points in the irreducible part of the
Brillouin zone (IBZ, 1/16 of the full zone for the bct lattice)
is done using the special k-point method. ' The fcc as well as
the bct crystal structure have been represented by a common
body-centered-tetragonal cell (for fcc this means a been performed up to about 50 GPa. The agreement between
c/a= Q2) so that the sampling of the zone is similar for the
two structures. More than 150 k points in the IBZ have been
used in the calculations. To ensure convergence in k space
the number of k points has, for the most compressed vol-
umes where the reciprocal space becomes largest, been in-
creased up to 484 in the IBZ. For the hcp crystal structure
(IBZ is 1/12 of the full zone for the hcp lattice) we used a
sampling density of 162 k points in the IBZ.
It has recently been shown that nonlocal corrections to the
local-density approximation, by means of the generalized
gradient approximation (GGA) for the exchange and corre-
lation functional, substantially improve the results for
f-electron systems. For that reason the GGA, according to
the recipe proposed by Perdew et al. , ' has been applied in
the present calculations. This has been done accurately with
the appropriate gradient terms evaluated for the full, non-
spherical electron density, see Appendix A.
The total energy (including core energy) was minimized
with respect to both volume and the axial ratio c/a, i.e. , an
energy surface was calculated as a function of the lattice
parameter and c/a. The calculations were self-consistent and
converged in energy down to about 10 p, Ry. The optimized
c/a value for a given volume was obtained by a least-squares
fit to an appropriate polynomial, for c/a values calculated on
a mesh with an increment of 0.03 in the c/a parameter. The
52
~ 40
C4
30—
20—
&0
20 22 24 28
Volume ( A )
FIG. l. Equation of state for Ce. Experimental results (Refs. 8
and 29) are marked with open squares, whereas theory is given by
a solid line.
atomic volume was successively decreased in steps of about
0.05 A in the lattice parameter. The theoretical pressure was
obtained from a numerical differentiation of the total energy
(minimized with respect to c/a).
III. EQUATION OF STATE
Before entering the details of the crystal structure of Ce
and Th under compression, we compare our calculated equa-
tion of state with experimental data for these two metals. In
Fig. 1 we show the theoretical and measured equation of
state for Ce. As mentioned above the theoretical equation of
state was calculated for the optimized crystal structure but in
the range where fcc was lowest in energy we obtained, from
a least-squares fit to the Murnaghan equation, Vo= 26. 1 A
and BO=49 GPa. Presently the measurements for Ce have
theory and experiment shown in Fig. 1 is good. There is a
small discrepancy at very low pressures which results in a
theoretical equilibrium volume which is approximately 7%
smaller than the measured low-temperature atomic equilib-
rium volume (28.0 A. ). This difference is comparable to
what is found for d transition metals. It has been shown that
the theoretical equilibrium volume for a-Ce is a quantity
most sensitive for the calculational details. The present cal-
culations for Ce, which assume itinerant 4f states, are how-
ever in good agreement with experiment and no additional
effects like the proposed Kondo screening seems to be
needed to obtain an accurate theoretical equilibrium volume
of n-Ce.
Thorium, which at ambient conditions has a 5f occupa-
tion that is considerably lower than the 4f occupation in
n-Ce, has a larger equilibrium volume than a-Ce. In Fig. 2
we show measurements of the equation of state for Th to-
gether with the present theoretical results. For Th the calcu-
lations give Vo=29.6 A and Be=63 GPa. This is to be
compared to the experimental values of Vo=32. 9 A and
Bo = 58 GPa. Just like for Ce, the experimental and theoreti-
cal data are in good agreement with each other. Comparing
the two metals we note that the theoretically obtained results
for n-Ce are in better agreement with experiment than the
results for Th.
52 THEORETICAL INVESTIGATION OF THE HIGH-PRESSURE. . . 13 171

400 expt
theory
350 20
300
~ 250 10
200
~ 06
~~ 150
0
~ 100
50 bQ
-10
fl n

I I I I

16 20 24 28 32 -20

Volume(A )
FIG. 2. Equation of state for Th. Experimental results (Ref. 10) -30
are marked with open squares, whereas theory is given by a solid I I I I I

line. 1000 1500 2000 2500 3000 3500

Pressure (GPa)
IV. CRYSTAL STRUCTURES
FIG. 4. Total energies for the bct (denoted with its c/a value),
For the metals Ce and Th we find it likely that a pressure- fcc, and hcp crystal structures relative to the bct (c/a = 1.65) struc-
f
induced increase of the occupation might lead to crystallo- ture as a function of calculated pressure. The bct structure
(c/a=1. 65) defines the zero level.
graphic phase transitions. We thus anticipate that crystal
structures which are typical for the other light 5f metals
might appear. Therefore, the body-centered-tetragonal struc-
ture, exhibited by Pa at ambient conditions, is a likely can- experimental and our calculated c/a ratio of the bct crystal
didate for a pressure-induced crystal structure of Ce and Th. structure as a function of compression for Ce. Experimen-
Indeed, as mentioned above, experimental observations of a tally, between -5 and 10 GPa there is an intermediate phase,
bct structure have been reported for both Ce (Ref. 8) and Th namely the base-centered-monoclinic structure (bcm "alled
(Refs. 9 and 10) at high pressures. In Fig. 3 we compare the the n" phase). In the experimental work by Olsen et al. it
was demonstrated that this phase is a slightly distorted bct
structure and therefore we find it appropriate to compare its
c/a ratio with out theoretical data for the bct structure. We
& expt have not tried to resolve the controversy whether this phase
1.75— is lowest in energy or if the n-U structure is the stable allot-
= theory
0 rop in the pressure range -5
and 10 GPa. ' At a pressure
1.7— U exceeding about 12 GPa, experiments show that Ce forms to
OWE the bct crystal structure with a c/a ratio of approximately
1.65— 1.65.
Our theoretical results for Ce, presented in Fig. 3, are
1.6— obtained by minimizing the total energy with respect to the
c/a ratio for the bct structure as a function of volume. With
1.55—
the representation of the experimentally observed a" phase
as an effective bct crystal structure, we notice a close simi-
1.5—
larity between theory and experiment as regards the pressure
1.45— dependence of the c/a ratio. The calculations show that the
fcc phase is stable at low pressures (c/a= Q2) and that a
C I I I I ! rather stable value of 1.65 for c/a is obtained for higher
0 10 20 30 40 50 60 70 80 90 100 pressures, with an intermediate region where c/a changes
Pressure ( GPa ) rapidly from Q2 to 1.65. It is interesting to notice that the
n" phase appears just in this intermediate region. At a pres-
FIG. 3. The c/a ratio for the bct structure as a function of sure above 20 GPa the theoretical data seem to be within the
pressure for Ce. Experimentally (Ref. 8) (marked with open error bars of the experimental data in Fig. 3 and our theory
squares) the intermediate phase (a") is approximated by a bct predicts that Ce remains stable in the bct phase (c/a close to
structure with an effective c/a ratio. Theoretical data (solid circle, 1.65) up to well above 500 GPa.
solid line) are plotted as a function of the calculated pressure. Figure 4 shows the ultrahigh pressure range of Ce (500—
13 172 SODERLIND, ERIKSSON, JOHANSSON, AND WILLS
1 7
1.65— ~ cqp rj ccrc& tj & &
1.6
~~ 1.55
V
1.5—
1.45—
I I I I I I I I
0 50 100 150 200 250 300 350 400
Pressure ( GPa )
FIG. 5. Experimental data (Ref. 9) (open squares) and theoreti-
cal results (solid circle, solid line) for the c/a ratio in the bct struc-
ture for Th as a function of pressure.
3500 GPa) as predicted by the present theory. We show the
energies of the bct structures [with c/a spanning from Q2
(fcc) to 1.60] and also the hcp crystal structure (ideal c/a)
relative to the bct structure with c/a = 1.65. As the pressure
increases above 500 GPa the c/a value in the bct crystal
structure is lowered, i.e., its value is approaching the fcc
value (c/a= Q2). At about 1600 GPa Ce transforms to the
hcp structure and this phase is found to be stable up to
—3500 GPa. At pressures lower than 1600 GPa, however,
the hcp form of Ce has a considerably higher energy than
both the fcc and bct crystal structures. For Ce we also inves-
tigate the energy dependence of the c/a value in the hcp
structure. Interestingly, for volumes where a tetragonal dis-
tortion of the fcc crystal structure (i.e. , a bct structure) low-
ered the energy, the energy was minimized for a distortion of
the c/a ratio (away from close packing) of the hcp structure
as well. However, for Ce the hcp structure was stable over
the bct structure only at pressures exceeding 1600 GPa and
for these high pressures the optimized c/a value of the hcp
structure was very close to the ideal value.
The behavior of the crystallographic phases of Th under
high compression (to be discussed in detail below) is very
similar to the behavior for Ce. This is expected since depend-
ing on pressure these two metals have similar occupationsf
and electronic structure. For a given pressure, however, the
occupation for Ce is considerably higher than for Th. We
also note here that at ambient conditions Ce and Th are
known from theory to have a very similar (small) tetrago-
nal shear constant. This particular elastic constant is relevant
for the phase transition from fcc to bct since it is exactly this
tetragonal deformation that transforms the fcc (c/a= Q2)
lattice into a bct (general c/a) lattice. A large tetragonal
shear constant (C') suggests that it is energetically very
costly to modify the c/a ratio, i.e. , an fcc — +bet phase transi-
tion is not anticipated in this situation.
In Fig. 5 we show the calculated and measured c/a ratio
as a function of pressure for Th. Experimentally, Th is stable
in its ambient pressure phase (fcc) for a pressure range up to
52
theory
d occupation
expt
f occupation
1.5
I I I I I
15 25 30
Volume (A )
FIG. 6. Calculated occupation numbers for the 5f and 6d partial
waves for Th as a function of compression.
63 GPa. For higher compressions Th is found to transform
continuously into the bct phase. Hence, Th displays a con-
tinuous crystallographic transformation from fcc to bct at 63
GPa. This is slightly different compared to the behavior of
Ce, where an intermediate crystal phase is observed. More-
over, the transition pressure is higher in Th. The theoretical
results in Fig. 5 confirm nicely this experimental observa-
tion, since a continuous change of the c/a ratio is obtained as
a function of pressure in our calculations. The theoretical
transition pressure is 45 GPa which is somewhat lower than
the experimental value. This discrepancy for Th is a reAec-
tion of differences between theory and experiments in the
equation of state (Fig. 2) for small compressions. We also
find that Th, like Ce, transforms to the hcp structure at even
higher compressions (data not shown).
V. DISCUSSION
Both Ce and Th undergo a crystallographic phase transi-
f tion upon compression from the fcc to the bct crystal struc-
ture, although for Th a higher pressure is needed to induce
the phase transition. Moreover, Ce attains an intermediate
o. " structure over a limited pressure range before the bct
structure appears. For both these metals there is an appre-
f
ciable increase of the occupation as a function of pressure.
This can partly be understood from the fact that the kinetic
energy becomes increasingly important for a metal under
compression and since the f
states have less radial nodes in
their wave function their kinetic energy is smaller than for
the other states in the valence band. Hence it follows that the
f band will move down in energy relative to the other bands.
To illustrate this we show in Fig. 6 occupation numbers for
Th obtained from LMTO calculations (in the atomic-sphere
52 THEORETICAL INVESTIGATION OF THE HIGH-PRESSURE. . . 13 173

5d
40—
fcc Ce
35—
30—
3
25—
2 20—
bQ
15—
C/} ~ 10-

0
Ct} 0-
0 5d

~ W
4 bet Ce 0.8 0.9 1 1, 1 1.2 1.3 1.4 1.5 1.6
c/a ratio

FIG. 8. Calculated Bain path for compressed Ce (22 A.~) close

to the transition pressure (10 GPa).

FF whereas in the bct structure the peak is essentially re-

moved, pushing weight of the 4f DOS towards lower ener-
gies. Thus this illustrates that the one-electron contribution to
the total energy minimizes the energy of the low-symmetry
structure. It is also clear from Fig. 7 that for Ce it is the 4f,
and not the 5d band, that provides the most important con-
I

-10 -5 0 5 10 tribution determining the fcc-bct energy difference, since the

Energy ( ev )
FIG. 7. Electron density of states (DOS) for the fcc and bct
(c/a = 1.65) structure for Ce at about 9 A and 700 GPa. The DOS
has been convoluted with a Gaussian function with 0.05 eV width.
approximation) and we note that the increased f
occupation
is associated with a decrease of all other orbital occupation
numbers, including the d's. The population of the f
band of
Th under high compression approaches the f
occupation of
Pa (bct) at ambient pressure and from this point of view it
seems natural that Th, for these occupations, adopts the bct
structure.
The onset of a low-symmetry crystal structure is due to
that a system with narrow f
bands can lower the energy by
"
lowering the symmetry of the crystal (Peierls distortion).
The explanation for this is that if the narrow f
bands are
lying close to the Fermi level (FF), this provides a situation
where the total energy can be lowered by the following
mechanism: Degeneracies of the f
bands, originating from
of the crystal structure, are lifted
symmetry requirements
when a lower symmetry of the crystal is introduced. If some
f
of the bands are shifted above the Fermi level (thus being
empty states and not influencing the ground-state energy)
and some other f
bands are shifted down to lower energies,
the total energy may be lowered. Hence, the energy of the
system can be decreased by this Peierls distortion. In Fig. 7
we illustrate the Peierls distortion by showing the calculated
electron density of states (DOS) for the symmetric (fcc) and
less symmetric (bct, c/a = 1.65) crystal structures of Ce at a
compressed volume. Note that in the fcc structure the narrow
4f bands result in a rather sharp peak at (or slightly above)
Sd DOS is quite broad and featureless for both structures
(this is of course also the case for the sp DOS not shown). —
f
Hence, for Ce (and Th) the increase of the occupation, as a
function of compression, tends to be unfavorable for the
symmetric fcc structure. At sufficiently high pressure (and
high f band occupation) the lowering of the one-electron
energy overcomes the increase of the electrostatic (Made-
lung) energy, connected to the lowering of the crystal struc-
ture symmetry. This analysis is similar to the discussion of
the crystal structure of Ce metal in the paper by Eriksson
et al. We thus argue that the f
occupation is an important
parameter for the determination of the crystal structures of
f
Ce and Th. Since the occupation is lower in Th compared
to Ce at ambient conditions, it may be understood that higher
pressures are needed before the fcc~bct phase transition is
induced in Th.
It is interesting to note that both Ce and Th show a bct
structure with a considerably larger c/a (c/a-1. 6) than
what is observed for Pa (c/a-0. 8). Since Ce and Th both
are fcc (bct with c/a= Q2) the bct structure with c/a of
about 1.6 is structurally much closer to the fcc structure than
the bct structure of Pa. Since the argument for the pressure-
induced onset of the bct structure is connected to a lowering
of the crystal structure symmetry (from fcc), it seems more
likely that Ce and Th becomes bct with a c/a larger than
Q2 rather than with c/a close to 0.8. In Fig. 8 we show the
calculated Bain path for Ce, i.e. , the energy variation as a
function of the c/a ratio in the bct structure, at a compressed
volume corresponding to a pressure slightly larger than the
transition pressure (10 GPa). The global minimum of the
energy appears for a c/a ratio of about 1.45 but there is also
a local minimum of the energy for a c/a ratio below 1.0
13 174 SODERLIND, ERIKSSON, JOHANSSON, AND WILLS 52

(bcc), which is rather close to the c/a ratio of Pa. This ob-
servation of a local minimum around c/a =0.85, which was
previously also found by Skriver, shows that also the struc-
ture of Pa would give a local minimum of the energy, but this
is not the ground state of the crystal.
As both cerium and thorium are compressed further, the
bands become broader due to the increased wave-function
overlap. This results in that the mechanism described above
for lowering the energy due to a Peierls distortion of narrow
bands becomes less important and the electrostatic (Made-
lung) energy drives the crystal to a higher symmetry. The
Madelung energy is about the same for the close-packed hcp
invariant under the point group of the crystal, are expressed
in the interstitial as a Fourier series,
(A 1)
f where the outer sum is over symmetry stars W of the recip-
rocal lattice and the inner sum is over vectors belonging to a
specific star. The gradient is applied on each term in the
series, and the resulting vector is inverse Fourier transformed
(to real space); scalar products are then evaluated in real
space. The double gradient Vn %~V'n~ is obtained from the
Fourier transform of V n ~, in the form of (Al), and n Simi-.
~

larly, the Laplacian V n is taken on each term of the Fourier

or fcc structures, as well as for the nearly close-packed bcc
series for n.
structure. Hence, it is the one-electron band energy that dis- Within the muffin-tin spheres, the calculation of density
tinguishes between the hcp, fcc, or bcc structures at ultrahigh gradients proceeds as follows. An invariant function f(r) is
compression. For close-packed structures it can be illuminat- expressed, in a muffin tin, as
ing to study the so-called l-projected canonical band
energies' which depend upon the crystal structure and not
the one-electron potential. In fact the canonical fbands f(r) = g f(h, r)Dg(r). (A2)
suggests that for an f occupation corresponding to both
cerium and thorium at high compression the hcp structure The sum in (A2) is over basis functions, Dq, for the invari-
should be favored over both the fcc and bcc crystal struc- ant representation of the local group of the atomic site con-
tures. This is in agreement with our self-consistent, full po- tained in the muffin tin. The basis functions Dh are linear
tential calculations. combinations of spherical harmonics; the Oh are real,
Finally we wish to emphasize that the present density- and we use the normalization f dxD&(x)D& (x)
functional treatment of the four valence electrons of Ce, in- = $4 sr/(2lq+ 1) 8(h, h'). Specifically,
cluding the 4f orbitals, is accurate in describing the high-
pressure crystallographic behavior in great detail as the
variation of the axial ratio, c/a, is an example of (a most Dz(r) = $4vr/(2lz+1)g n (h)i'~I'~ (r), (A3)
sensitive crystallographic parameter). The closely related be-
havior of thorium metal at high pressure strongly suggests where the n are orthonormal within an 1 manifold. The
that there is no fundamental difference in the behavior of the
Ce 4f and the Th Sf electrons. Thus compressed cerium
scalar product of the gradients of two invariant functions
and g is an invariant and can be expressed as in (A2):
f
shows a crystallographic behavior which demonstrates that
cerium under these conditions has to be characterized as an
itinerant (metallic) f-electron system. ' V'f(r) V'g(r) = F(r) = g F(h, r)—
D„(r), (A4)

2l„+1~ t'

ACKNOWLEDGMENTS
F(h, r) = 47r
'

dxD&(x)F(x). (AS)

We thank J. Trygg for critical reading of the manuscript
and valuable discussions. A. K. McMahan is acknowledged
for valuable discussions. B. Johansson and O. Eriksson are
thankful for financial support from the Swedish Natural Sci-
ence Research Council as well as from the Materials Con-
sortium. We are grateful to the Swedish National Supercom-
puter Center (NSC) in Linkoping for supplying some of the
computer time used in this project. Work performed under
the auspices of the U. S. Department of Energy by the
Lawrence Livermore National Laboratory under Contract
No. W-7405-ENG-48.
The radial coefficients F(h, r) in (A4) can be calculated nu-
merically from the derivatives of the radial coefficients of the
invariant functions f and g, combined with a set of generic
coefficients; the calculation of these coefficients is described
below. Invariants derived from scalar products of gradients
are calculated in this way. The Laplacian V' n is constructed
directly from the series (A2). All radial derivatives are cal-
culated by numerical differentiation.
The calculation of the radial coefficients of a scalar prod-
uct of gradients is as follows. Taking the gradient of f(x) in
(A2) results in

(A6)
APPENDIX A
In this appendix, we describe the calculation of the den- where
sity gradients necessary for the evaluation of the GGA en-
ergy and potential.
' In the interstitial, the process is straight-
forward. Functions, such as the electron density n(x), (A7)
52 THEORETICAL INVESTIGATION OF THE HIGH-PRESSURE. . . 13 175

4~ —
f, (h, r) =
2Ih+1)
~('

(
r
a
Br
+ l„+ 1 f(h, r), (A8) Vf(r) Vg(r)=F(r)=g F(h, r)Dh(r),

4mr
and
F(h, r) = g ft, (h', r)

Dk(h, r) = Q(2lh+ k+ 1)i8mg n (h)i'"Yt t +k (r). x g g„(h", r)W(k'k";h'h"h),

(A9)
(Alo)
Y is a vector spherical harmonic. Then where (l'=l„, etc).

H(k'k";h'h "h) = dxD~, (h', x) D„n(h", x)Dh(x)

(A11)
(2l'+k'+ li (2l" +k" + li"
8m 8
t(2(l'+ k')+ 1)(2(l"+ k")+ 1)]'"
I
t

(k'+t. ")/2~
(l'+k' l" +k" l) (l' l" l) ' l l' l"
0 0 0( i 0 0 Oj 1 I +k" l'+0'

&& g
mm
t m'ft
rr*, (h') n (h") n*(h) 9'(1', m';l", m";l, m), l'+ l" + l even;

=0, l'+l +l odd, (A13)

and X'is related to the Gaunt coefficient: To be strict, each product (like V'n~ ) should result in an
~

increase in the appropriate cutoff parameter [the maximum

reciprocal-lattice vector in (Al) or the maximum l value in

=i' ' +',

K(l', m';l", m";l, m)

2l+ 1
~
1/2 &

dxYt (x) Y,*„„(x)Y, (x).

(A14)
(A2)]. We do not account for this; cutoff parameters inherited
from the charge density are preserved through each product.
Since our total energies are substantially converged with re-
spect to these cutoffs, this truncation should not have an
appreciable effect.

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