The strain

Definitions
In CRYSTAL, the effect of strain is defined as follows:
- The cartesian axes remain unchanged
- The cartesian components of a vector r transform as follows:

In particular, if A is the matrix containing the cartesian components of the three elementary
translation vectors, a
1,
a
2
and a
3



The strained matrix, A' is:
A' = (1+s) A

The symmetry of the elastic tensor and Voigt notation
The tensor [sJ can be decomposed into two parts:
- an antisymmetric part, [[J, that corresponds to a pure rotation

- a symmetric part, [sJ, that corresponds to a pure strain (without rotational components)


Then, if we are interested only in the strain part of the transformation, we can refer to the
following pure strain tensor:

As only six components of the symmetric matrix are independent, a more compact one-index
notation can be adopted.
Let us define, according to Voigt's convention:






In this convention the strain tensor becomes:


and can be expressed as a vector:

The ZnO case
To illustrate the effect of strain, we will use the ZnO wurtzite structure (hexagonal 6mm class).
The ZnO cell parameters are:

a=3.2859 c=5.2410

The three direct lattice vectors are labelled a
1
, a
2
, a
3
; E F K are, as usual, the angles between a
2

and a
3
, a
1
and a
3
, a
1
and a
2
, respectively. The convention adopted in CRYSTAL for the a
1
and a
2

orientation is given in figure 1. The cartesian components of a
1
and a
2
are reported. The A
matrix, is given on the right.


Figure 1: Hexagonal cell of wurtzite in the (xy) plane, according to CRYSTAL convention.


As a first example, let's apply the following strain to ZnO:


The A matrix is modified by the strain into A'







= a

= a

E' = 90
0

F' = 90
0

K' = 120
0


Figure 2: Deformation of the ZnO hexagonal cell, when the strain s is
applied.
The undistorted and distorted cells are represented in light and dark
grey, respectively. The volume variation is also represented in dark
grey. The new lattice parameters are reported on the right side of the
figure.

As a second example consider:


From A', it is easily seen that = a, = c; E = F = 90
0

For and K' we get:

For small H values, we can disregard terms quadratic in H, so that we get for and K' (use a
Taylor expansion):

and or in degrees.
For H = 00l (a typical value we will use in the following), A|a
1
| = -0.43 and AK = 01o .

In summary (length in and angles in degrees; variation percentage is also given in
parentheses):
I)






a'
1
=3.2718
(-0.43)

E '= 90
0
(0.00)

a'
2
=3.2859
(0.00)

F' = 90
0
(0.00)

a'
3
=5.2410
(0.00)

K'=119.57
0
(-0.36)

We can consider now the effect of deformations II, III and IV, closely related to the one just
discussed. It turns out that II has the same effect as I, to first order, and III is simply the
superposition of I and II; IV is a pure rotation (again to the first order; actually the modulus of
the a' lattice parameter changes 2 . 10
-4
), so that the translation vectors and the angles between
them do not change. This means that we can use, alternatively, I or II or III; their effect is, to
first order, exactly the same; for example, the energy difference, AE with respect to the
unstrained case, is shown in the following figure. AE for deformation IV is null to first order.
The choice among I, II and III will be eventually dictated by symmetry considerations.




Figure 3: Variation of ZnO total energy (in mhartree) when the four
strain tensors I, II, III, IV (see text) are applied. The energy
difference A E
0,I
or A E
0,II
are 3.35 10
-4
hartree, whereas the second
order differences ( A E
0,IV
or A E
I,II
) are of the order 10
-7
, 10
-8
.
Note that A E
0,III
is four times H ( AE is proportional to (2H)
2
and
H
2
, see the elastic section below).

II)






a'
1
=3.2717
(-0.43)

E '= 90
0
(0.00)


a'
2
=3.2861
(0.00)

F' = 90
0
(0.00)


a'
3
=5.2410
(0.00)

K'=119.57
0
(-0.36)

III)






a'
1
=3.2575
(-0.86)

E '= 90
0
(0.00)


a'
2
=3.2861
(0.00)

F' = 90
0
(0.00)


a'
3
=5.2410
(0.00)

K'=119.14
0
(-0.72)

IV)






a'
1
=3.2861
(0.00)

E '= 90
0
(0.00)


a'
2
=3.2861
(0.00)

F' = 90
0
(0.00)


a'
3
=5.2410
(0.00)

K'=120
0
(0.00)
The elastic tensor
Definitions
The elastic constants are second derivatives of the energy density with respect to strain
components:

where V is the volume of the cell and |c| is a rank 4 tensor with 3 x 3 x 3 x 3 = 81 elements
(called constants).
As seen before, the strain s can be expressed with a single index (i=1,6), using Voigt's notation.
The elastic constants then become:

with i,j=1,6. It is obvious from the definition that this matrix is symmetric, so the elastic tensor
has a maximum of 21 independent elements.
The elastic tensor and the symmetry
Due to the symmetry of the crystal, some of the constants are zero, or symmetry related. In order
to know which independent components must be considered, a preliminary run (a TESTGEOM
run) must be performed using the TENSOR keyword. CRYSTAL output indicates which
constants are independent, and the coefficients relating the symmetry equivalent constants.
How to proceed
A Taylor expansion of the unit cell energy to second order in the strain components yields:

If E(0) refers to the equilibrium configuration, the first derivatives are zero. According to
equation (2), the elastic constants can then be obtained by evaluating the energy as a function of
strain.
The energy derivatives can be evaluated numerically (CRYSTAL03) or analytically
(CRYSTAL06), with respect to the cell parameters.
When the unit cell is deformed (using the ELASTIC option), the point group may be reduced to
a subgroup of the original point group (see examples below). The new point group is
automatically selected by the code. For each deformation of the unit cell, the atoms must be
allowed to relax (In some cases this relaxation is not necessary, as the atoms occupy special
positions). The optimization is performed by using the OPTGEOM option (see manual).
The ZnO case
To illustrate the calculation of an elastic tensor, we will continue to detail the ZnO wurtzite
example.
First of all, in order to know which are the independent tensor components, we run the crystal
executable with the following geometry input:
ZnO wurtzite elastic tensor
CRYSTAL
0 0 0
186
3.2859 5.2410
2
30 0.66666666666667 0.3333333333333 0.
8 0.66666666666667 0.3333333333333 0.38268
TENSOR
4
TESTGEOM
END
The wurtzite compounds have the 6mm hexagonal symmetry. The TENSOR directive produces
the following output:
THIS ROUTINE EVALUATES THE NON ZERO ELEMENTS
OF TENSORS OF PHYSICAL PROPERTIES UP TO ORDER 4

ORDER OF THE TENSOR : 4

| 1 A 1 E 1 B . . . |
| 1 A 1 B . . . |
| 1 D . . . |
| 1 C . . |
| 1 C . |
| & |

EACH LETTER CORRESPONDS TO AN INDEPENDENT COMPONENT.
INTERDEPENDENT COMPONENTS (WITH SAME LETTER) ARE RELATED BY
THE COEFFICIENT THAT PRECEDES EACH LETTER.

THE "&" SYMBOL MEANS 1/2(C11-C12) (OR 2(S11-S12)) FOR THE ORDER
4 C AND S ELASTIC TENSORS IN THE TRIGONAL OR HEXAGONAL CASES.
The number of independent terms in various tensors, in particular for the elastic and piezoelectric
tensor can be found in standard textbooks, for example in Nye[1]. These tables must be used
with some care, because the structure of the tensor depends on the adopted convention for the
orientation of the cartesian axes with respect to the unit cell vectors. The output of the TENSOR
routine might show permutation with respect to standard definitions[1])
There are only 5 independent components (5 different letters) to evaluate:
A: c
11
= c
22

B: c
13
= c
23

C: c
44
= c
55

D: c
33

E: c
12


The symbol & indicates that c
66
can be deduced from two independent components [c
66
= ~ (c
11
+

c
12
)]. This particular case happens for trigonal and hexagonal systems only.
To define the complete elastic tensor, 5 different strains must be applied. The c
ij
constants can be
separated in two groups:
- Diagonal terms. They are directly related to second derivatives of the energy.
- Off-diagonal terms. The second derivative is obtained by at least two deformations.
The diagonal terms
c
11


The [ J tensor for the calculation of c
11
is:

The energy expression is:

where a and b are the coefficients of a polynomial fit of E versus H (see examples below). Then
(see equation (2));

c
33


The [ ] tensor for the calculation of c
33
is:

The energy expression is:

Then:

c
44


The [ ] tensor for the calculation of c
44
is:

NB: In Voigt's notation
The energy expression is then:


Then

The off-diagonal terms

c
12


The [ ] tensor for the calculation of c
12
is:

The energy expression is:

The output of TENSOR shows that c
11
= c
22
(and c
12
= c
21
by definition), then


Then
(c
11
+

c
12
) = b/V


c
13

The [ J tensor for the calculation of c
13
is:


The energy expression is:

Then
(~c
11
+

~c
33
+c
13
) = b/V
Computational conditions
To obtain E as a function of a given , the energy must be computed for various H (the strain
amplitude). Particular care is required in the selection of the computational parameters and of the
points where the energy is evaluated, in order to avoid large numerical errors in the fitting
procedure.
As regards computational conditions:
- All the calculations were performed with the same "reference" geometry (the undistorted
one) for the selection of integrals, by using the FIXINDEX option.
- The point group may reduce to a subgroup. Then internal relaxation of the atoms may be
necessary. In this case, high accuracy is required in the convergence criterion of the
optimization. The following options were used to modify the default values (see
OPTGEOM option):

OPTGEOM
TOLDEG
0.00006
TOLDEX
0.00012
TOLDEE
8
ENDOPT
(default values, are less severe, namely 0.0003, 0.0012 and 7)
- Very high accuracy is also needed in the SCF step:
- TOLDEE
- 10
The default value used in CRYSTAL06 for standard SCF is 5 (see manual).
The fitting
In the example below, referring to c
33
, 15 runs have been performed (with the strain presented
above) with -0.035 < H < 0.035 and step 0.005.
The table included in figure 3 gives the 15 energy points that are fitted with polynomials of
various degrees. The value of the second derivative, b, of the fitted function at the equilibrium
geometry, is presented in Table 1 . It turns out that, in the explored interval, the first acceptable
polynomial must contain a fourth order component (H

). The best value is around 1.3625. When

the explored interval is reduced, eliminating one or two points from each side (second and third
row of Table 1), the b value remains essentially the same.
H E
-0.035
-0.030
-0.025
-0.020
-0.015
-0.010
-0.005
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
-3705.43936297
-3705.43980354
-3705.44017696
-3705.44048292
-3705.44072111
-3705.44089138
-3705.44099328
-3705.44102736
-3705.44099326
-3705.44089111
-3705.44072094
-3705.44048301
-3705.44017760
-3705.43980510
-3705.43936571
Figure 4: Energy, E (in hartree), for the 15 H values, of ZnO. Data are shown to the left;
the fitting curve is an order 3 polynomial; the energy (in mhartee) has been shifted by
3705.442 hartree.

Table 1: Value of the b parameter as a function of the number of points N and order of the
polynomial P. The stability domain of b is boxed.
N
\ P
2 3 4 5 6 7
15 1.35779 1.35779 1.36276 1.36276 1.36240 1.36240
13 1.35861 1.35859 1.36279 1.36275 1.36214 1.36200
11 1.35910 1.35971 1.36274 1.36243 1.36213 1.36142


This scheme must be repeated for the other four strains previously presented. Some of the strains
decrease the number of symmetry operators, implying higher computational costs. For each
strain here considered Table 2 gives the number of symmetry operators, the relationship between
the second order term b and the elastic constants and the fitted b value (as in Table 1 ).

Table 2: Number of symmetry operators, N, second order term, b, of the energy fit and
relationship between b and the elastic constants, for the five strains here considered. The
equilibrium volume, V, is 49.0065
3
.
s
N b

4 1.384


12 1.363


2 1.260


12 4.203


4 3.940


The five elastic constants are deduced from Table2. If the volume and the energy are in
3
and
hartree, respectively, the obtained constants are in hartree/
3
; to get them in GPa, multiply by the
conversion factor 4359.74812.
The full (symmetric) elastic tensor of ZnO obtained at the HF level is then (in GPa):

Very often it is useful to obtain the so called elastic moduli tensor [S], which is the inverse of [C]
the elastic constants tensor:
CS = SC = I

In the present case we obtained (in pPa
-1
):

Experimental data are available in this case for comparison and are reported in Table 3.

Table 3: Comparison of calculated and experimental elastic constants (in GPa). Variation
percentage of the HF method with respect to experiment is also reported.
c
11
c
33
c
44
c
12
c
13

HF 246.2 242.5 56.0 127.7 106.2
% +17.8 +12.3 +26.7 +6.4 +1.7
exp
2
209.0 216.0 44.2 120.0 104.4

As expected, the Hartree-Fock hamiltonian tends to overestimate the second derivative of the
energy.
Exploiting the point symmetry
With the previous form of the s matrix the number of point symmetry operators is reduced to 4,
whereas the following s matrix maintains the full point symmetry (12 operators):

The energy expression is:

Then
(c
11
+

~c
33
+c
12
+2 c
13
) = b/V

The piezoelectric tensor
Definitions
The piezoelectric constant e
ikl
is defined, to first order in the strain[2,3], through:

(1)

then

(2)

where P
i
is the polarisation along the cartesian i axis and the derivative is evaluated at zero
strain.
As seen before, the strain s can be expressed with a single index (j=1,6), using Voigt's notation.
The piezoelectric constants are then expressed as:

(3)


with i=1,3 and j=1,6; the piezoelectric tensor contains then a maximum of 3 x 6 =
18 independent elements.
The piezoelectric tensor and the symmetry
Due to the symmetry of the crystal, some elements of this rank 3 tensor are null, or
interdependent (as in the elastic tensor case). The TENSOR option gives the independent
constants and the coefficients to connect the inter-related ones (see also [1]).
How to proceed
In order to avoid a multivalued problem[3,2], the polarisation is not computed directly, rather we
evaluate the related phase (the Berry phase) in the reciprocal lattice vector basis. Then, the
proper piezoelectric constant is deduced as follows:

(4)
where V and a
il
are the undistorted unit cell volume and component along the cartesian axis i of
the a
i
direct lattice vector, respectively.
According to equation (4), the piezoelectric constants can be obtained by evaluating the phase as
a function of deformations of the unit cell parameters. Note that the A matrix, contains the three
translation vectors ordered as:
.
The "PARET" matrix, that appears in the crystal output, is the transpose of A.
The computational scheme can be decomposed in 4 steps:
1. As in the elastic tensor case, when the unit cell is deformed , the point group is reduced to
a subgroup of the original point group. Following the deformation of the unit cell,
internal relaxation of the atoms may be necessary (depending on the space group
symmetry; then use OPTGEOM to optimize the structure).
2. The Berry phase is computed for each strain, using the keyword POLARI in a properties
run.
3. This phase has no physical meaning. The difference with respect to a reference (the
undistorted one is usually chosen) has to be computed (properties with the keyword
PIEZOBP).
4. Data are fitted and the final calculations are performed.
The computational conditions are the same as for the elastic constants. Actually, the different
strains that must be applied in order to compute the complete piezoelectric tensor (a maximum of
six strains), are also required for the elastic tensor, so that the piezoelectric tensor can be seen as
a by-product of the calculation of the elastic tensor. Step 1 is then common with the elastic tensor
calculation. Steps 2., 3. and 4. are fast; the additional cost, with respect to the elastic tensor
calculation, is very small. Extra strains, performed in the elastic case, can be used as "cross
checks"
The ZnO case
As in the elastic case, to know which are the independent components of the [ ] tensor, we use
the following geometry input:
ZnO wurtzite piezoelectric tensor
CRYSTAL
0 0 0
186
3.2859 5.2410
2
30 0.66666666666667 0.3333333333333 0.
8 0.66666666666667 0.3333333333333 0.38268
TENSOR
3
TESTGEOM
END
The keyword TENSOR produces the following output:
THIS ROUTINE EVALUATES THE NON ZERO ELEMENTS
OF TENSORS OF PHYSICAL PROPERTIES UP TO ORDER 4

ORDER OF THE TENSOR : 3

| . . . . 1 A . |
| . . . 1 A . . |
| 1 B 1 B 1 C . . . |

EACH LETTER CORRESPONDS TO AN INDEPENDENT COMPONENT.
INTERDEPENDENT COMPONENTS (WITH SAME LETTER) ARE RELATED BY
THE COEFFICIENT THAT PRECEDES EACH LETTER.

In this case, the piezoelectric tensor is composed by only 3 independent terms:
A: e
15
= e
24

B: e
31
= e
32

C: e
33

To get the full piezoelectric tensor 3 strains are required.

e
33


The [ J tensor for the calculation of e
33
is:

(5)

By applying equation (4) to this case:

(6)

Then

(7)

where a
3l
is the component along z of the lattice vector a
l
. As mentioned before, in our case the
third row of the A matrix (containing the z components of the three translation vectors) is (0, 0,
c).
Then

(8)

It is to be noticed that each strain s produces three phases o
l
, o
2
, o
1
and then provides three
piezoelectric constants e
1i
, e
2i
, e
3i
,. In the present case (s
i
s
1
), two of them (e
13
and e
23
) are zero
by symmetry (see the TENSOR output); we can however compute them to check whether they
are actually null, in order to have a measure of numerical noise. Applying equation (6), we get:

(9)

and

(10)

When the elements of the A matrix are used, we get:

(11)
and

(12)



Figure 5: Phase difference o
l
, o
2
, and o
1
with respect to H = 0 as a
function of H
Table 4 gives the values of the phase difference o
l
, o
2
, and o
1
with respect to H = 0 along the
three reciprocal lattice vectors b
1
, b
2
, and b
3
.

Table 4: The phase, o
i
, along the three reciprocal vectors b
i
, for the 15 H values considered.

H o
l
o
2
o
1

-0.035 0.000004 0.000004 -0.189461
-0.030 -0.000001 0.000010 -0.158187
-0.025 0.000008 0.000009 -0.128346
-0.020 -0.000004 0.000017 -0.099903
-0.015 0.000015 0.000013 -0.072879
-0.010 0.000012 0.000009 -0.046978
-0.005 -0.000001 0.000010 -0.022921
0.000 0.000000 0.000000 0.000000
0.005 -0.000014 0.000023 0.021157
0.010 -0.000023 0.000001 0.041188
0.015 -0.000016 -0.000002 0.059617
0.020 0.000013 -0.000003 0.076505
0.025 0.000020 -0.000006 0.092376
0.030 0.000010 -0.000014 0.106365
0.035 0.000015 -0.000016 0.118843


At this point we must evaluate the derivative of the 3 curves (presented in figure 5) at H = 0. The
derivatives of o
l
and o
2
are null, as clearly seen from the figure. For the derivative of o
1
,
polynomials of various order were used (as in the evaluation of the b term for the elastic
constants). Results are reported in table 5.

Table 5: as a function of the number of points P and order of the polynomial P.


P 2 3 4 5 6 7
N
15 4.408516 4.416939 4.416938 4.410543 4.410552 4.408524
13 4.411208 4.414471 4.414474 4.408827 4.408834 4.411157
11 4.412884 4.410961 4.410970 4.412133 4.412120 4.398272

The best value is:

(13)

The piezoelectric constant is then obtained from equation (8) as follows.



The prefactor is automatically calculated at the end of the PIEZOBP (and PIEZOWF)
output, following the phase results:
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%

PHASE PROJECTED ALONG THE RECIPROCAL LATTICE VECTORS
B1 B2 B3
PHI -0.000014 0.000023 0.021157

PREFACTOR: |e|/(2.PI.VA)= 0.05203314E+10(C/m**3)

TTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTT PIEZOBP CPU 0.080

e
31


The [ ] tensor for the calculation of e
31
is:

(15)


Table 6 gives the values of the phase difference o
l
, o
2
, and o
1
with respect to H = 0; o
1
is
plotted in figure 6.
Table 6: The phase, o, along the three reciprocal directions i , for the 15 H values considered.
H o
l
o
2
o
1

-0.0175 -0.000014 0.000015 0.077271
-0.0150 -0.000011 0.000011 0.065452
-0.0125 -0.000006 0.000008 0.053811
-0.0100 -0.000010 0.000013 0.042448
-0.0075 0.000000 -0.000004 0.031564
-0.0050 -0.000008 0.000004 0.020437
-0.0025 -0.000001 0.000002 0.009939
0.0000 0.000000 0.000000 0.000000
0.0025 -0.000007 -0.000004 -0.010015
0.0050 -0.000014 0.000002 -0.019502
0.0075 0.000007 -0.000012 -0.028640
0.0100 -0.000009 0.000001 -0.037339
0.0125 0.000003 -0.000008 -0.045669
0.0150 -0.000019 0.000006 -0.05398
0.0175 -0.000018 -0.000003 -0.061655

Let us see how to compute e
31
; according to equation (3) we get:

(16)

Since e
31 =
e
32
(see TENSOR output), we have:

(17)

In the present strain tensor s, s
l
= s
2
= H and s
1
= 0; then:

(18)
so:

(19)

As mentioned before, in order to avoid a multivalued problem, the polarisation is not computed
directly, rather we evaluate the related Berry phase. Then, e
31
is deduced as follows:

(20)

where a
31
is the component along z of the lattice vector a
i
. As mentioned before, in our case the
third row of the A matrix (containing the z components of the three translation vectors) is (0, 0,
c).
Then

(21)
Two other terms, e
11
and e
21
, can be obtained applying the same strain ; but they are null by
symmetry (see the TENSOR output) and will not be considered.


Figure 6: Phase difference o
1
with
respect to H = 0 as a function of H.

The derivative of the figure 6 curve at H = 0 is:

(22)
The derivatives of o
l
and o
2
are null (figures are not reported but equivalent to the s
1
case).
The piezoelectric constant is then obtained from equation (21) as follows.


e
24


The [ ] tensor used for the calculation of e
24
is:

(24)


Table 7 gives the values of the phase difference, o
l
, o
2
, and o
1
, with respect to H = 0; o
l
and o
2

are plotted on figure 7.
Table 7: The projected phase, o
l
, o
2
, and o
1
(along the reciprocal vectors b
1
and b
2
), plotted for
the 15 H values considered.

H o
l
o
2
o
1

0.0000 0.000000 0.000000 0.000000
0.0025 -0.000004 -0.012387 -0.000024
-0.0025 -0.000009 0.013890 0.000670
0.0050 0.000010 -0.025240 -0.000075
-0.0050 0.000014 0.026489 0.001333
0.0075 -0.000007 -0.038484 0.000613
-0.0075 0.000006 0.039689 0.000407
0.0100 -0.000007 -0.051556 0.001110
-0.0100 0.000015 0.052273 0.002200
0.0125 -0.000006 -0.064639 0.001785
-0.0125 -0.000004 0.065635 0.002450
0.0150 -0.000008 -0.077544 0.002067
-0.0150 -0.000010 0.078852 0.002046
0.0175 -0.000001 -0.090596 0.002833
-0.0175 -0.000005 0.091924 0.002834

Let us see how to compute e
24
; according to equation (4) we get:

(25)

where a
21
is the component along y of the lattice vector a
l
. In our case the second row of the A
matrix (containing the y components of the three translation vectors) is (-~a, a, 0).
Then

(26)



Figure 7: Phase difference o
l
and o
2
with respect to H = 0 as a
function of H.

The derivative of the figure 7 curves at H = 0 are:

(27)


(28)

The derivative of o
1
is null (figure is not reported). The piezoelectric constant is then obtained
from equation (26) as follows:


The full piezoelectric tensor of ZnO obtained at the HF level is then (in C/m
2
):

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Table 8: Comparison of calculated and
experimental piezoelectric constants (in C/m
2
).
Variation percentage of the HF method with
respect to experiment is also reported.

e
31
e
33
c
24

HF -0.543 1.203 -0.444
% +12.4 +25.3 -16.7
exp
5
-0.62 0.96 -0.37

Experimental data are available in this case for comparison and are reported in Table 8.
Exercises
The following exercises are classified in basic ( ) or advanced ( ) levels.
Exercise 1
( )
Find the new direct lattice vector matrix, A', and deduce the new lattice parameters, , ,
, E', F' and K', when the following strain is applied:

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to the undistorted ZnO A matrix:

(32)

Solution


Only the z component of the direct lattice vector is modified by the strain. As a
consequence,

=a

=a

E' = 90
0
F' = 90
0
K' = 120
0


Exercise 2
( )
Construct the first two points (the smallest H values on each side of the undistorted reference
geometry) of a ZnO input series containing the following generic strain:

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Our set of data contains 15 points (including the undistorted one) with -0.035 < H 001 and
step 0.035.
A starting input of ZnO can be found in ZnO.d12
Note that the reference geometry, is the undistorted one (FIXINDEX keyword).


Solution

ZnO wurtzite elastic tensor
CRYSTAL
0 0 0
186
3.2859 5.2410
2
30 0.66666666666667 0.3333333333333 0.
8 0.66666666666667 0.3333333333333 0.38268
ELASTIC
-2
0. 0. 0.
0. 0. 0.
0. 0. 0.005
.
.
.
END

Exercise 3
( ) ( )
Find the new direct lattice vectors matrix, A', and deduce the new lattice parameters (as a
function of H), when the following strain is applied:

(35)

Simplify the obtained new cell parameters just keeping terms linear in H.

Solution





=a



= 90
0





To the first order of delta, we have:

=
a

= a

= c
E
=
90
0

F

K
=
120
0



Exercise 4
( )
Run the elastic tensor symmetry analysis for BeO wurtzite, adding the TENSOR keyword in the
BeO file (BeO.d12).
In the directory exercise4/out are the outputs generated by applying the following strain:

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with 15 different H values (-0.035 < H 001). The energy data are in exercise4/out/res.dat.
Use the shell script elastic to find, b, the second order term of the energy fitting.
Write then the relation between b and the elastic constant c
33
. Finally deduce the value of c
33

(in hartree/ and in GPa ).
Note that the undistorted cell volume can be found in each output.
Solution
THIS ROUTINE EVALUATES THE NON ZERO ELEMENTS
OF TENSORS OF PHYSICAL PROPERTIES UP TO ORDER 4

ORDER OF THE TENSOR : 4

| 1 A 1 E 1 B . . . |
| 1 A 1 B . . . |
| 1 D . . . |
| 1 C . . |
| 1 C . |
| & |

EACH LETTER CORRESPONDS TO AN INDEPENDENT COMPONENT.
INTERDEPENDENT COMPONENTS (WITH SAME LETTER) ARE RELATED BY
THE COEFFICIENT THAT PRECEEDS EACH LETTER.

THE "&" SYMBOL MEANS C11-C12 (OR 1/2(S11-S12)) FOR THE ORDER
4 C AND S ELASTIC TENSORS IN THE TRIGONAL OR HEXAGONAL CASES.


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Then

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Exercise 5
( ) ( )
NaNO
2
is an orthorhombic compound. Run its elastic tensor symmetry analysis (the basic input
for NaN0
2
can be found in exercise5/NaNO2.d12. How many strains are necessary to compute
the full elastic tensor? Propose a set of strains, and in each case the relation between the second
order term, b, of the energy fit, and the elastic constants.


Solution

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(41)



(42)



(43)



(44)


Exercise 6
( )
In the directory exercise6/out are stored the outputs of the strain:

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The Berry phase has been calculated for 15 H values ranging from -0.035 to +0.035 (step of
0.005) with respect to the undistorted structure (point1, H = 0). The phase results are stored in
the file exercise6/out/res.dat . Use the shell script piezo to plot the phase, o, along the three
reciprocal directions, as a function of H. Write down the relationships between the slop of the
three curves and the three piezoelectric constants e
13
, e
23
and e
33
; then deduce their values (in
C/m
2
).


Solutions

Exercise 7
( )
In the directory exercise7/out are stored the outputs of the strain:

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The Berry phase has been calculated for 15 H values ranging from-0.0175 to 0.0175 with respect
to the undistorted structure (point1, H = 0). The phase results are stored in the file
exercise7/out/res.dat . Use the shell script piezo to plot the phase, o, along the three reciprocal
directions, as a function of H. Write the relationship between the slop of the three curves and the
three piezoelectric constants e
15
, e
25
and e
35
; then deduce their values (in C/m
2
).