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Energy band structure of gold

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1970 J. Phys. C: Solid State Phys. 3 S1

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 A supplement to
JOURNAL OF PHYSICS C
SOLID STATE PHYSICS
VOLUME 3

METAL PHYSICS
No. 1 May 1970

Energy band structure of gold

M. G. RAMCHANDANI
Bhabha Atomic Research Centre, Chemistry Division, Trombay, Bombay 85, India
M S . received 23rd January 1969, in revised form 11th August 1969

Abstract. The energy band structure of metallic gold has been calculated by non-rela-
tivistic and relativistic augmented plane wave methods. The E(k) against k curves are
plotted for some directions of high symmetry. The conduction band is an s-d mixture.
The density of states curves are plotted. The results are compared with available experi-
mental and other theoretical data on the band structure of gold.

1. Introduction
The first elaborate band structure calculations using the augmented plane wave (a.p.w.)
method proposed by Slater (1937) were made by Burdick (1963) for copper thereby estab-
lishing the power of this technique. Since then a large number of band structure calculations
have been reported by others on different elements. Loucks (1967) has given a list of metals
for which a.p.w. calculations have recently been made. Snow and Waber (1967) and Snow
(1968 a, b) have recently made self-consistent non-relativistic a.p.w. energy band structure
calculations on copper and silver. Loucks (1967) has maintained that for metals having
atomic numbers greater than about 71, the relativistic effects become prominent. He has
developed the relativistic augmented plane wave method (Loucks 1965 a, 1966)which he has
applied to tungsten (Loucks 1965 b) and lead (Loucks 1965 a).
Even though much work has been reported on noble metals such as copper and silver,
no ab initio complete band structure calculations have been made for gold. Cooper et al.
(1965) have described the experimental results on optical properties of gold. Mande (1960)
has described x-ray work on gold. Also extensive data are available on the shape and size
of the Fermi surface of gold (Morse 1960, Shoenberg 1960).The present work describes two
sets of complete energy band structure, Fermi energy and the density of states calculations
for gold via non-relativistic and relativistic a.p.w. methods. A comparison is made with
available data from experiments and other theoretical calculations.
2. Theory
The theory of both the relativistic as well as the non-relativistic a.p.w. method is given
in detail by Loucks (1967). The calculations were made on a CDC-3600 computer. Pro-
grams were based on those given by Loucks (1967). The non-relativistic a.p.w. programs
were tested by making energy band calculations for points along one symmetry axis in the
s1
s2 M . G. Ramchandani
Brillouin zone for copper. These results coincided with the initial results of Snow and
Waber (1967).
3. Potential
The potential used in the present calculations is the standard muffin-tin type, that is
spherically symmetric inside the a.p.w. spheres and constant in space outside the spheres.
The a.p.w. sphere radius was so chosen to be equal to one half the nearest-neighbour
distance in the face-centred cubic lattice. The crystal potential was constructed by a super-
position (Mattheiss 1964)of the atomic potentials from up to the 14th nearest neighbours in
the face-centred cubic lattice. The atomic potentials used in calculating the crystal potential
were from the self-consistent Dirac-Slater calculations made by Liberman et al. (1965).
Snow and Waber (1967) and Snow (1968 a, b) have tried different exchange potentials and
report that 2 Slater exchange gives better results ; however, the present calculations were
done taking unit Slater exchange. The radial mesh employed was a logarithmic scale, the
starting point of which was chosen to -8.647 523 for the non-relativistic case and
- 8.651 114 for the relativistic case (since the lattice constants for the two cases are different) ;
an interval of mesh of 0.05 was used.
4. Non-relativistic calculation
Gold has a lattice constant equal to 4.0786 A (American Society for Testing Materials,
Philadelphia powder diffraction file). The a.p.w. sphere radius obtained is 2.725 a.u. The
constant potential outside the a.p.w. sphere is found to be -1.0535 ryd. The muffin-tin
potential is so adjusted as to make this constant potential zero.
Taking 1 values up to 6 the logarithmic derivatives R’(l, E)/R(l, E ) were found, where
R(1,E ) is the solution of the radial Schrodinger equation for fixed 1 and E, 1 being the orbital
quantum number and E the energy in ryd. As expected, these derivatives differ from the
free-electron case in that there is no discontinuity for I = 0 when plotted against energy.
However, the logarithmic derivative for gold resembles that of copper and has discontinuity
for I = 2 at E = 0.64 ryd.
The energy eigenvalues were computed for 89 points in & of the Brillouin zone. From
these, the energy eigenvalues for 2048 uniformly distributed points of the Brillouin zone were
obtained by the application of symmetry properties. The points in the Brillouin zone are
labelled according to their symmetry in the standard BSW way (Bouchaert et al. 1936). The
present calculations were up to 0.82 ryd for some points whereas for most points the lower
limit was used. The aim was to locate the Fermi energy and so the region below and

Figure 1. Non-relativistic energy bands for gold. Energies are in rydbergs and constant
potential outside the a.p.w. spheres is zero.
 Energy band structure of gold s3
immediately above it was carefully scanned. The eigenvalues were obtained by finding the
zeros of the 32 x 32 determinant. Figure 1 gives the plot of energy curves in certain sym-
metric directions.
To locate the Fermi level, the energy eigenvalues for each point in the Brillouin zone
were labelled in increasing order of magnitude. In the case of gold the states arising from
up to 5p levels of the atom will be completely filled. Only 5d and 6s levels of the atom are
expected to form the conduction band. Hence while finding the Fermi energy we take into
account only the ten d electrons and one s electron per atom. Since each energy level can
accommodate two electrons of opposite spin, the first 5.5 x 2048 = 11 264 energy levels
will be occupied and all higher energies will be unoccupied. The Fermi energy is found to
be 0.713ryd. To this we should add the constant potential and we obtain
E , = 0.713 - 1.0535 = - 0.3405 ryd = - 4.638 eV.
The density of states is defined as half the number of electrons per unit energy interval
(in eV) per atom. The number of electrons per electron volt per atom is plotted against the
energy (figure 2). The histogram has the bar width of 0.005ryd and is an average of five
different histograms of bar width 0,025 ryd.

01 /-- I 1 1 I 1 1 1 1 8
0.066 0,266 0.466 0.666kf 0.81 6
Energy (ryd)
Figure 2. Non-relativistic histogram for the number of electrons per atom per electron
volt. Energies are in rydbergs.

5. Relativistic calculations
The relativistic calculations are made in accordance with Louck’s (1967) theory. The
lattice constant was chosen to be 7.6799 a.u. This lattice constant has been used by Jacobs
(1968).The maximum value of ti (see Loucks 1967, chapter 4, equation 4.78) was taken to be
s4 M . G. Ramchandani

Table 1. The relativistic energy eigenvalues for various points in the Brillouin zone

BSW Energy eigenvalues in rydbergs

symbol k Band 1 Band 2 Band 3- Band 4 Bind 5- Band6 Band7
r 000 -0.157 0.134 0.134 0.231 0.300 0.300
A 010 -0.143 0.132 0,137 0.233 0.303 0.3 10
A 020 -0.105 0.125 0,148 0.242 0.292 0.319
A 030 - 0'047 0.1 10 0.161 0.261 0,286 0.334
A 040 0.0 10 0.090 0.186 0.288 0,301 0.356
A 050 0.031 0.069 0.249 0.318 0.344 0.386
A 060 0.024 0.052 0.321 0.345 0,420 0.432
A 070 0.0 13 0.041 0.359 0.371 0.45 1 0.562
X 080 0.0 10 0.039 0.372 0.389 0.469 0.645 0.978
c 110 -0'130 0.133 0.138 0.236 0.295 0.303
120 - 0,093 0.127 0.147 0.245 0.289 0323
130 - 0.037 0,113 0.158 0,265 0,283 0.343
140 0.0 19 0.094 0.176 0.291 0.298 0.372
150 0.040 0.074 0.224 0.323 0,340 0.4 15
160 0~032 0.058 0.284 0.353 0.396 0.490
170 0.021 0.048 0.329 0,374 0.436 -
z 180 0.018 0.046 0.354 0,381 0.455 -
z 220 - 0,058 0.127 0.148 0.255 0.280 0,339
230 - 0.007 0.119 0.153 0.270 0.273 0.369
240 0.045 0.105 0.158 0.285 0.297 0.414
250 0.066 0.090 0.184 0.320 0.332 0.476
260 0.056 0.076 0.229 0.349 0,379 -
270 0.044 0.068 0.270 0.364 0.4 18 -
280 0.041 0.067 0.297 0.366 0.438 -

330 0.035 0.121 0.154 0.259 0.283 0.414

340 0.077 0.118 0.155 0.265 0,304 0.472
350 0,098 0.1 10 0,159 0.299 0.334 0.548
360 0.087 0.104 0.183 0.331 0.372 -
370 0.073 0.101 0.214 0.342 0.410 -
Z 380 0.069 0.102 0.234 0.342 0.429 _-
z 440 0.096 0122 0.176 0.253 0.319 0.541
450 0.100 0.125 0.181 0.277 0.344 -

460 0.095 0.129 0.180 0.309 0.376 -

470 0.086 0.135 0.186 0.323 0.410 -

W 480 0.085 0.140 0.192 0.329 0.429 -

z 550 0.084 0.140 0.208 0.278 0.361 -

560 0.073 0.139 0.218 0.305 0.387 -
570 0.069 0.132 0.224 0.328 0.4 16 -

K 660 0.053 0.128 0.258 0.322 0.404 -

A 111 - 0.1 18 0.135 0.138 0.240 0.297 0.315

121 - 0.082 0.130 0.146 0.249 0.289 0.325
131 - 0'028 0.118 0.155 0.261 0.291 0.347
141 0.025 0102 0.169 0.275 0.322 0.379
151 0.045 0.083 0.211 0.300 0.370 0.428
161 0.038 0.066 0.268 0.33 1 0,412 0.518
171 0.028 0.056 0.314 0.358 0.438 -
 Energy band structure of gold s5

BSW -Energy eigenvalues in rydbergs-

symbol k Band 1 Band 2 Band 3 Band 4 Band 5 B a n d 6 Band7
S 181 0.026 0.054 0.340 0.370 0.448 -
22 1 - 0.05 1 0.134 0.147 0.254 0.288 0.339
23 1 - 0.005 0.130 0.154 0.256 0.298 0.368
241 0.038 0.121 0.160 0.264 0.330 0.412
25 1 0.057 0.106 0.185 0.287 0.374 0.480
26 1 0.055 0,088 0.227 0.318 0.408 -

271 0.048 0,077 0.267 0.343 0.428

28 1 0.047 0.075 0.219 0.356 0.434 -
33 1 0.025 0.134 0.166 0.249 0,305 0.4 10
341 0.054 0.131 0.176 0.254 0,328 0468
351 0.074 0.122 0.179 0.279 0.364 0,545
361 0.080 0.110 0.193 0.308 0.396 -

371 0.075 0.105 0.2 17 0.328 0.416

381 0.074 0.106 0.233 0.337 0,425
44 1 0.069 0.129 0.206 0.248 0.337
45 1 0.084 0.123 0.206 0.27 1 0.361 -

46 1 0.094 0,118 0,198 0.298 0.389 0.470

Q 47 1 0.092 0.127 0.193 0.317 0.41 1 .-

551 0.079 0.131 0.222 0.277 0.373

561 0.074 0.134 0.220 0,301 0.395 .-

A 222 - 0,029 0.140 0.155 0.251 0.303 0,344

232 0.000 0,138 0.175 0.247 0.323 0.370
242 0.030 0.136 0.183 0.251 0.365 0.415
252 0.050 0.125 0.192 0.268 0.402 0303
262 0.058 0,109 0.218 0.29 1 0.422 -

272 0.058 0.099 0.249 0.315 0.427

U 282 0.060 0,097 0.267 0.335 0.422 -
332 0.012 0.136 0.214 0.244 0.338 0.399
342 0.029 0.134 0.219 0.258 0367 0.459
352 0.049 0.129 0.212 0.270 0.400 0.556
362 0.068 0.121 0.213 0.284 0.416 __
372 0078 0.118 0.221 0.301 0.418 -
442 0.037 0.132 0.225 0,284 0.368 0,576
452 0.053 0.128 0.225 0.287 0.390 -

Q 462 0.076 0,121 0.220 0.286 0.405

552 0.060 0.128 0.230 0,290 0.395 -
A 333 0.008 0.134 0.228 0.294 0,368 0.398
343 0.0 16 0.133 0.224 0.315 0.399 0.456
353 0.034 0.132 0.221 0.299 0.417 0393
363 0.059 0.130 0.223 0.283 0.420 -

443 0.016 0.132 0.222 0.345 0.405 0.510

Q 453 0.030 0.133 0,223 0.328 0.412 0,593
L 444 0.0 10 0.134 0224 0.386 0.437 0.482 0.776

In order to obtain the correct energy for a given k the value of constant potential between
spheres ( - 1.0653 ryd) must be added to the listed value. For listed values of k see Burdick (1963).
S6

Figure 3. Relativistic energy bands for gold. Energies are in rydbergs with constant
potential outside the a.p.w. sphere set equal to zero.

2.750-

i relativistic

Figure 4. Relativistic histogram for the number of electrons per atom per electron volt.
Energies are in rydbergs.
 Energy band structure of gold s7

seven. As in the non-relativistic case a discontinuity is found in the logarithmic derivative

when plotted against energy for both positive and negative K. The energy eigenvalues are
found by obtaining the zeros of a 24 x 24 determinant. The eigenvalues for different points
of the Brillouin zone are tabulated in table 1 and plotted in some symmetry directions in
figure 3. Fermi energy obtained is 6.92 eV as against the free-electron model value of 5.5 eV.
The number of electrons per atom per electron volt is plotted against energy in figure 4.

6. Discussion
Chatterjee and Sen (1968)have calculated energy eigenvalues for gold at a few symmetry
points of the Brillouin zone by the quantum-defect method. Table 2 provides a comparison
between their values and the present calculations.
Jacobs (1968) has calculated the band structure for the noble metals using the Korringa-
Kohn-Rostoker method. A comparison for some points for gold is given in table 3.
Table 2
Points (1) (2) (3)
rs - 1.0122 -0’988 - 1.222
xs - 0’3278 - 0.507 - 0.596
XP - 0.3636 -0515 - 0‘676
Ls --0’5857 - 0.542 - 0.679
LP - 0.4409 - 0.452 - 0528
(1) Chatterjee and Sen (1968); (2) present non-relativistic;
(3) present relativistic. All energies are in ryd.

Table 3
(1) (2) (3)
Xk-X5 0348 0.240 0.176
r25,-r1 0.191 0234 0.291
xi-r , 0.703 0.721 0.802
x,--r, 0355 0.48 1 0.626
X,-& 0.271 0.405 0.430
X, upper--X, - 0,770 0.509
L, upper-L; 0.368 0,486 0,294

(1) Jacobs (1968); (2) present non-relativistic; (3) present rela-

tivistic. All energies are in ryd.

6.1. Fermi suface

Shoenberg (1962) has measured the size of the Fermi surface of gold. He reports that the
Fermi surface touches the Brillouin zone on the hexagonal faces. The present calculations,
both relativistic and non-relativistic, confirm this.
The Fermi surface is given explicitly by the equation
E(k) = E,.
The Fermi energy was found as described earlier. E, contours of constant energy have been
found in three planes, namely (loo), (1 10) and the hexagonal plane (1 11). This was done
for both non-relativistic and relativistic cases. The contours for Ef are shown in figure 5
for the relativistic case. The contours for the non-relativistic case are almost similar. The
striking features of the Fermi surface are (i) a neck on the hexagonal face and (ii) a deviation
from spheres in the belly region.
The shape of the Fermi surface is in agreement with the experiments of Shoenberg (1962),
Roaf (1962) and Morse (1960). Table 4 gives a comparison between experimental and cal-
culated values of some of the Fermi surface parameters.
S8 M . G. Ramchandani

Table 4
( 1) (2) (3) (4)
Belly radius along T-K 1.21 1.2 1.149 1.182
Belly radius along T-X 1.26 1.435 1.392 1.417
Neck radius 0.22 0.228 0.287 0.222
(1) Morse(1960);(2) Shoenberg(l962)and Roaf(1962);(3)present non-relativistic;
(4) present relativistic. All the values are in p units (10- l9 gm cm s- I).

6.2. Thermal data

The number of electrons per atom per electron volt (twice the density of states) at Fermi
energy is found to be 0.620 for the non-relativistic case and 0.303 for the relativistic case. The
electronic specific heat coefficient ^J values for the two cases are 3.473 x and
1.697 x loT4cal mol-' deg Cn2. Martin (1964) and Du Chatenier and De Nobel (1962)
have given experimental values of y to be 1.74 x and 1.76 x lop4cal mol-' deg C2.

6.3. X-ray data

The x-ray absorption spectra reveal the nature of the unoccupied part of the conduction
band while the emission spectra reveal the nature of the occupied part of the band. Mande
(1960) has studied absorption and emission of x-rays for gold. The width of the occupied

4,;;;;;/
\ '
r
I( //

Figure 5. Intersection of Fermi surface with (a) hexogonal face ( l l l ) , ( b ) (100) plane
and (c) (1 10) plane. Relativistic calculations.
 Energy band structure of gold s9
conduction band reported by him is 8.1 eV. The present non-relativistic calculations give
this to be 8,798 eV (non-relativistic) and 9.696 eV (relativistic). While Mande reports the
peak of the band to be 5.0 eV below the Fermi energy, in the present calculations the highest
peak is found to be 5.3 eV below the Fermi energy in the non-relativistic case and 5.64 eV
for the relativistic case.
Acknowledgments
I should like to thank Dr P. G. Khubchandani for his kind encouragement during the
progress of this work. I am grateful to Dr T. L. Loucks for clarifying some of my doubts
regarding his computer program and to Dr D. Liberman for supplying me with his self-
consistent atomic potential calculations. I am indebted to Shri G. Mukhopadhyay for
the many useful discussions I had with him while carrying out this work.

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COOPER, B. R., EHRENREICH, H., and PHILIPP,H. R., 1965, Phys. Rev., 138, A 494-507.
Du CHATENIER, F. J., and DE NOBEL,J., 1962, Physica, 28, 181--3.
JACOBS, R. L., 1968, J . Phys. C: Proc. Phys. Soc., 1, 1296-306.
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1. PHYS. C : M E T A L PHYS. S U P P L . , NO. 1. 1970. P R I N T E D I N GREAT B R I T A I N