Last Modified 17 December 1999

The ``Static'' Tight-Binding Program: Example X

Equation of State and equilibrium configuration of hcp Titanium for fixed c/a


In the Equation of State (EOS) section we found E(V) for Titanium by minimizing the total energy at each volume with respect to the c/a ratio. This gives us the true equation of state, but we can ask the question ``what happens if we keep a fixed value of c/a?'' The answer, of course, depends upon the precise value of c/a chosen. For our purposes here, we'll set c/a equal to the equilibrium value of c/a found in the EOS,

(c/a)0 = 1.61326030   .

(Okay, this is overkill, I admit.)

Let e(V) = E(V,(c/a)0), the energy at any volume using the equilibrium c/a ratio, and

E(V) = E(V,(c/a)(V)), the energy calculated in the EOS section and the minimum energy at a give volume.

Then we know that

e(V) > E(V)

except at V = V0, the equilibrium volume for both e(V) and E(V), where
E0 = E(V0) = e(V0)   .

It follows from this that the equilibrium bulk modulus derived from e(V) is greater than the true bulk modulus:

b(V0) = V0 e''(V0) > V0 E''(V0) = B0   .

If we go through the derivation of b(V) from e(V), we find that in terms of the elastic constants,

b(V) = 1/9 [ 2 (C11 + C12) + C33 + 4 C13 ]   .

In this section we'll determine e(V) = E(V,(c/a)0) as a function of volume, and then use the Birch fit to calculate b(V0). This will give us our second relationship between elastic constants.

The setup is reasonably simple. Since we are not changing the symmetry of the crystal we can use the same space group file, work/spcgp1.hcp and k-point mesh, work/kmesh.194. Of course we use the same tight-binding parameters, which are stored in work/ti_par. The only thing new is the SKIN file, work/fixca/SKIN. You'll notice that this SKIN file contains every volume used in the final EOS determination, but in every case the c/a ratio is 1.61326030.

Running the calculation in the work/fixca directory, we get the following results:

$ static > output
$ ls -l
-rw-r-----   1 mehl     users        1134 Jun  4 14:41 SKENG
-rw-r-----   1 mehl     users       13124 Jun  4 14:38 SKIN
-rw-r-----   1 mehl     users       51120 Jun  4 14:41 SKOUT
-rw-r-----   1 mehl     users       39727 Jun  4 14:41 output

Since we know e(V) and E(V) are identical at V0, we can use the same fitting procedure here as in the EOS calculation, with only a very slightly modified work/fixca/hcpfit2.gnu gnuplot fitting file.

$ gnuplot hcpfit2.gnu
Fit set for vo = 220.088 Bohr^3 and
Eo = -0.009018141 Ry.  Change hcpfit2.gnu if necessary.
Press Enter to continue
Equilibrium Volume = 220.088 Bohr^3 = 32.613683827428 Angstroms^3
Equilibrium Energy = -0.009018141 Ry
Equilibrium Bulk Modulus = 0.00829452139631914 Ry/Bohr^3 = 122.016693030704 GPa
dB/dP (P=0) = 3.81463566444934
Press Enter to end program
$

We see that the bulk modulus is just a bit larger than in the true EOS calculation (122.02 vs 121.74 GPa). The total energy plot is very similar, too, so I'll leave that for you to plot out.

Finally, the result of this section is that

1/9 [ 2 (C11 + C12) + C33 + 4 C13 ] = 122.0 GPa   .


Go back to the Example X home page.

Look at other examples.

Get other parameters from the Tight-binding periodic table.


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