CRYSTAL Tutorial Project - Elastic and Piezoelectric Tensors.

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The evaluation of the elastic and piezoelectric

tensors
Y. Noel and R. Dovesi

The strain
Definitions
The symmetry of the elastic tensor and Voigt notation
The ZnO case
The elastic tensor
Definitions
The elastic tensor and the symmetry
The ZnO case
The diagonal terms
The off-diagonal terms
Computational conditions
The fitting
Exploiting the point symmetry
The piezoelectric tensor
Definitions
The piezoelectric tensor and the symmetry
The ZnO case
Exercises
Elastic and piezoelectric constants using scripts
multdef
elastic
piezo
Bibliography
List of available input decks and output files

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, a1, a2 and a3

The strained matrix, A' is:

A' = (1+e) A

The symmetry of the elastic tensor and Voigt notation

The tensor [e]] can be decomposed into two parts:
 an antisymmetric part, [w], that corresponds to a pure rotation

a symmetric part, [e], 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 a1, a2, a3; a, b, g are, as usual, the angles between a2 and a3, a1 and a3, a1 and a2,
respectively. The convention adopted in CRYSTAL for the a1 and a2 orientation is given in figure 1. The cartesian components of a1 and
a2 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

a' = 900
b' = 900
g' = 1200

Figure 2: Deformation of the ZnO hexagonal cell, when the strain e 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; a = b = 900

For and g' we get:

For small d values, we can disregard terms quadratic in d, so that we get for and g' (use a Taylor expansion):
 and or in degrees.

For d = 0.01 (a typical value we will use in the following), D|a1| = -0.43% and Dg = -0.36% .

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

I) a'1=3.2718 a'2=3.2859 a'3=5.2410

(-0.43) (0.00) (0.00)

a '= 900 b' = 900 g'=119.570

(0.00) (0.00) (-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, DE with
respect to the unstrained case, is shown in the following figure. DE 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 D E0,I or D E0,II are
3.35 10-4 hartree, whereas the second order differences ( D E0,IV or D EI,II) are
of the order 10-7, 10-8 . Note that D E0,III is four times d ( DE is proportional to
(2d)2 and d2, see the elastic section below).

a'1=3.2717 a'2=3.2861 a'3=5.2410

(-0.43) (0.00) (0.00)
II)
a '= 900 b' = 900 g'=119.570
(0.00) (0.00) (-0.36)

a'1=3.2575 a'2=3.2861 a'3=5.2410

(-0.86) (0.00) (0.00)
III)
a '= 900 b' = 900 g'=119.140
(0.00) (0.00) (-0.72)
 a'1=3.2861 a'2=3.2861 a'3=5.2410
(0.00) (0.00) (0.00)
IV)
a '= 900 b' = 900 g'=1200
(0.00) (0.00) (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 e 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: c11 = c22

B: c13 = c23

C: c44 = c55

D: c33

E: c12

The symbol & indicates that c66 can be deduced from two independent components [c66 = (c11 + c12)]. This particular case happens
for trigonal and hexagonal systems only.

To define the complete elastic tensor, 5 different strains must be applied. The cij 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

c11

The [ ] tensor for the calculation of c11 is:

The energy expression is:

where a and b are the coefficients of a polynomial fit of E versus d (see examples below). Then (see equation (2));
 c33

The [ ] tensor for the calculation of c33 is:

The energy expression is:

Then:

c44

The [ ] tensor for the calculation of c44 is:

NB: In Voigt's notation

The energy expression is then:

Then

The off-diagonal terms

c12

The [ ] tensor for the calculation of c12 is:

The energy expression is:

The output of TENSOR shows that c11 = c22 (and c12 = c21 by definition), then
Then
(c11 + c12) = b/V

c13

The [ ] tensor for the calculation of c13 is:

The energy expression is:

Then
(c11 + c33+c13) = b/V

Computational conditions
To obtain E as a function of a given , the energy must be computed for various d (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 c33, 15 runs have been performed (with the strain presented above) with -0.035 < d < 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 (d4). 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.

d E
-0.035 -3705.43936297
-0.030 -3705.43980354
-0.025 -3705.44017696
-0.020 -3705.44048292
-0.015 -3705.44072111
-0.010 -3705.44089138
-0.005 -3705.44099328
0.000 -3705.44102736
0.005 -3705.44099326
0.010 -3705.44089111
0.015 -3705.44072094
0.020 -3705.44048301
0.025 -3705.44017760
0.030 -3705.43980510
0.035 -3705.43936571
Figure 4: Energy, E (in hartree), for the 15 d 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.

e 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.

c11 c33 c44 c12 c13

HF 246.2 242.5 56.0 127.7 106.2

% +17.8 +12.3 +26.7 +6.4 +1.7

exp2 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 e matrix the number of point symmetry operators is reduced to 4, whereas the following e matrix maintains
the full point symmetry (12 operators):

The energy expression is:

Then

(c11 + c33+c12+2 c13) = b/V

The piezoelectric tensor

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

(1)

then

(2)

where Pi is the polarisation along the cartesian i axis and the derivative is evaluated at zero strain.

As seen before, the strain e 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 ail are the undistorted unit cell volume and component along the cartesian axis i of the ai 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: e15 = e24
B: e31 = e32
C: e33

To get the full piezoelectric tensor 3 strains are required.

e33

The [ ] tensor for the calculation of e33 is:

(5)

By applying equation (4) to this case:

(6)

Then

(7)

where a3l is the component along z of the lattice vector al. 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 e produces three phases j1, j2, j3 and then provides three piezoelectric constants e1i, e2i, e3i,. In the
present case (ei e3), two of them (e13 and e23) 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 j1, j2, and j3 with respect to d = 0 as a function of d.

Table 4 gives the values of the phase difference j1, j2, and j3 with respect to d = 0, along the three reciprocal lattice vectors b1, b2, and
b3.

Table 4: The phase, ji , along the three reciprocal

vectors bi, for the 15 d values considered.

d j1 j2 j3

-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 d = 0. The derivatives of j1and j2 are null, as
clearly seen from the figure. For the derivative of j3 , 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

e31
The [ ] tensor for the calculation of e31 is:

(15)

Table 6 gives the values of the phase difference j1, j2, and j3 with respect to d = 0; j3 is plotted in figure 6.

Table 6: The phase, j, along the three reciprocal

directions i , for the 15 d values considered.

d j1 j2 j3

-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 e31; according to equation (3) we get:

(16)

Since e31 = e32 (see TENSOR output), we have:

(17)

In the present strain tensor e, e1 = e2 = d and e3 = 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, e31 is deduced as follows:
 (20)

where a31 is the component along z of the lattice vector ai. 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, e11 and e21, 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 j3 with

respect to d = 0 as a function of d.

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

(22)

The derivatives of j1 and j2 are null (figures are not reported but equivalent to the e3 case). The piezoelectric constant is then obtained
from equation (21) as follows.

e24

The [ ] tensor used for the calculation of e24 is:

(24)
Table 7 gives the values of the phase difference, j1, j2, and j3, with respect to d = 0; j1 and j2 are plotted on figure 7.

Table 7: The projected phase, j1, j2, and j3 (along the reciprocal
vectors b1 and b2), plotted for the 15 d values considered.

d j1 j2 j3

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 e24; according to equation (4) we get:

(25)

where a21 is the component along y of the lattice vector al. 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 j1 and j2 with respect to d = 0 as a function of d.

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

(27)

(28)

The derivative of j3 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/m2):

(30)

Table 8: Comparison of calculated and experimental

piezoelectric constants (in C/m2). Variation percentage of
the HF method with respect to experiment is also
reported.

e31 e33 c24

HF -0.543 1.203 -0.444

% +12.4 +25.3 -16.7

exp5 -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, , , , a', b' and g', when the following

strain is applied:

(31)
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

a' = 900 b' = 900 g' = 1200

Exercise 2 ( )

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

(34)

Our set of data contains 15 points (including the undistorted one) with -0.035 < d < 0.035 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 d), when the following strain is
applied:

(35)

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

Solution

=a

= 900

To the first order of delta, we have:

=a =a =c

a = 900 b g = 1200

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:

(37)

with 15 different d values (-0.035 < d < 0.035). 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 c33. Finally deduce the value of c33 (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 ( ) ( )

NaNO2 is an orthorhombic compound. Run its elastic tensor symmetry analysis (the basic input for NaN02 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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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 d values ranging from -0.035 to +0.035 (step of 0.005) with respect to the undistorted
structure (point1, d = 0). The phase results are stored in the file exercise6/out/res.dat . Use the shell script piezo to plot the phase, j,
along the three reciprocal directions, as a function of d. Write down the relationships between the slop of the three curves and the three
piezoelectric constants e13, e23 and e33; then deduce their values (in C/m2).

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 d values ranging from-0.0175 to 0.0175 with respect to the undistorted structure (point1, d
= 0). The phase results are stored in the file exercise7/out/res.dat . Use the shell script piezo to plot the phase, j, along the three
reciprocal directions, as a function of d. Write the relationship between the slop of the three curves and the three piezoelectric constants
e15, e25 and e35; then deduce their values (in C/m2).

Elastic and piezoelectric constants using scripts

Scripts can be downloaded here

multdef
In the calculation of the elastic and piezoelectric tensor, many crystal (and properties) runs are required; for each strain, , the energy
and the Berry phases j1, j2 and j3 will be computed, at many values. From case to case, the input differs only in a few lines. In order to
automate the creation and run of inputs, (and avoid typing errors), a script, multdef, can be used. The scheme of this cshell script is
shortly described below.

The multdef script refers to the environment variables defined in cry2k6.cshrc

CRY2K6_ROOT CRYSTAL06 root directoy

CRY2K6_ARCH ARCH string to identify the executable
CRY2K6_SCRDIR temporary directory for scratch files
CRY2K6_EXEDIR binaries directory
CRY2K6_INP "crystal" input files directory $here default $here
CRY2K6_PROP "properties" input files directory default
MPIBINDIR Path to the MPI binary files (for parallel execution)

Variables inside the control file

For each type of strain, a control file should be created in the $CRY2K6_INP directory. It contains keywords and the associated values.
Few keywords are mandatory; most of the optional keywords have default values given in parentheses.
Strain controls
Next_pt required Next point that the script has to consider (automatically incremented by the script)
Total_pt required Number of point to consider
Delta_max required Maximum value
Strain_mat required The strain matrix. It is given in unit of >, three values per line.
List_pt List of points that will be considered (not numerical order)
Nblist_pt (0 ) Number of points in the list
CRYSTAL controls
Crystal (True) Execute the wave function calculation.
Guessp (True) Inserts the GUESSP keyword in the SCF input (block3, SCF guess from external file).
Fixindex (True) Inserts the FIXINDEX keyword in the input (block3, integrals classification from reference geometry).
Optimization controls
Optgeom (True) Activates the internal parameters optimization.
When OPTGEOM is active, allows restarting from a previous Hessian matrix (keyword HESGUESS in the OPTGEOM
Hesguess (True)
input file).
Toldex (0.00012) Modify the optimization convergence threshold on displacement.
Toldeg (0.00006) Modify the optimization convergence threshold on gradient.
Toldee (8 ) Modify the optimization convergence threshold on energy .
Piezo controls
Runs properties (after crystal) to compute the Berry phase (or the localised Wannier functions, see next
Piezo (True)
keyword) with respect to the undistorted structure, in order to compute the piezoelectric constants.
Use the Berry phase scheme (CRYSTAL keyword POLARI) to compute the piezoelectric constants. If False,
BP (True)
the localised Wannier functions are used(CRYSTAL keyword LOCALWF)
IS (4 ) Shrinking factor used in properties to recompute the eigenvectors (CRYSTAL keyword NEWK)

Here is the control file used to compute the ZnO elastic constant c33, and the piezoelectric constant e33 (using Wannier functions) ,
through the strain:

with 15 values -0.035 < < 0.035

This is a comment in the control file
Current_pt = 1
Total_pt = 15
Delta_max = 0.035
Strain_mat
0. 0. 0.
0. 0. 0.
0. 0. 1.
BP = False LWF scheme used (This is also a comment)

Comments can be added (if they DO NOT contain keywords) after the value of a keyword, or alone on a line.

Short description of the multdef structure

Infinite LOOP
Read control
 IF (Current_pt Total_pt)
Update control
Construction of the input
Run crystal
IF (Piezo is True)
Run properties with the POLARI (default) keyword.
ENDIF
ELSE
EXIT_LOOP
ENDIF
END_LOOP
IF(Piezo is True AND All points done)
Final calculations: Run properties with the PIEZOBP keyword.
Write a summary of the results in res.dat
ENDIF

elastic

The elastic script

Input : the res.dat file that is written at the end of the multdef script
Output : a postscript file res_e.ps
It contains :

Table 1 : the data table ( and E in hartree)

Table 2 : table containing the second derivative of the energy with respect to the strain times 2/V (in GPa), as a function of the
fitting polynomial order
Figure 1 : the E = f( ) fitted curve

Syntax : elastic [-oX] [-t{text}] [-s] res.dat

Three options are available :

-oX To modifiy the fitting polynomial order used on Figure 1 (default X=3).
-t{text} To put text as title on the output page (text can be any LATEX string).
-s To activate silent mode (no output of the host machine and directory)

piezo
Syntax : piezo res.dat
Input : the res.dat
Output :
Page 1 : the data table ( , j1, j2 and j3) and in another table the value as a function of the order of the fit and a last table that gives

the 3 deduced piezoelectric constants (for simple strains) only.

Page 2-4 : For each reciprocal direction i, the ji = f( ) fitted curve.

Bibliography
1
J.F. Nye,
Physical properties of crystals.
Oxford (1985).
2
R.D. King-Smith and D. Vanderbilt, ``Theory of Polarization of Crystalline Solids'',
Phys. Rev. B 47, 1651 (1993).
3
R. Resta, ``Macroscopic Polarization in Crystalline Dielectrics: The Geometric Phase Approach'',
Rev. Mod. Phys. 66, 899-915 (1994).

4
Landolt-Bornstein (Editor: O. Madelung), ``Low Frequency Properties of Dielectric Crystals: Elastic Constants,''
New Series, Group III: Solid State Physics, Vol. 29a, Springer-Verlag, Berlin (1993)

5
Landolt-Bornstein (Editor: O. Madelung), ``Low Frequency Properties of Dielectric Crystals: Piezoelectric, Pyroelectric and Related
Constants''
New Series, Group III: Solid State Physics, Vol. 29b, Springer-Verlag, Berlin (1993)
6
E.E. Tokarev, I.B. Kobyakov, I.P. Kuz'mina, A.N. Lobachev, and G.S. Pado,
Sov. Phys. Solid State 17, 629 (1975)

Footnotes

... evaluate1
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].
... exp2
: Ref. []
... respectively.3
Note that the A matrix, whose components are aij contains the three translation vectors ordered as:
. The "PARET" matrix, that appears in the crystal output, is the transpose of A.

... reference4
For details on the fortran units to save and use in the successive runs, see the PIEZOBP keyword.
... exp5
: Ref. []
... values2
The boolean values true and false can be indifferently written lower or upper case (or mixed).
... optimization.3
Attention! If there is no free internal parameter (for symmetry reasons), crystal stops at the beginning of the calculation (without
producing a density matrix file).

List of available input decks and output files

Here a list of the available input decks is reported. In some cases the corresponding output files are also available.

Directory Input Output Description

ZnO zno.d12 ZnO input file for CRYSTAL

BeO beo.d12 BeO input file for CRYSTAL

exe4_inputs.zip exe4_outputs.zip Exercise 4: control file for multdef and

corresponding CRYSTAL inputs/outputs created
by the script

NaNO2 nano2.d12 NaNO2 input file for CRYSTAL

exe6_inputs.zip exe6_outputs.zip Exercise 6: control file for multdef and

corresponding CRYSTAL inputs/outputs created
by the script

exe7_inputs.zip exe7_outputs.zip Exercise 7: control file for multdef and

corresponding CRYSTAL inputs/outputs created
by the script