EN.510.

633 Computational Materials Design - Lab 1

Ahmed M. Hussein February 28, 2011

1
By running the given input le in GULP, which describes a gold crystall and does phonon calculations, the zero point energy at zero temperature was found to be 0.0556 eV and the free energy was found to be 15.0606 eV .

2
In order to compute the thermal expansion coecient, one needs to nd the minimum free energy conguration at dierent temperature and constant pressure. The control variable is the lattice parameter which changes as the temperature changes. Then, using the relation 1 V (2.1) V T one can make an estimate for the thermal expansion coecient. For the case in hand, the dierentiation is done numerically between the two temperatures 283K and 293K (which correspond to 10o C and 20o C respectively. For each case, dierent lattice parameters were used and the minimum free energy was sought. The lattice parameters ranged from 4.0784 to 4.16 in varying A A step sizes. At the beginning, a coarse step size of 0.0016 was used for both temperatures in order to frame A the minimum free energy conguration, later, recursively ner step sizes of 0.0008, 0.0004, 0.0002 and A A A 0.0001 were used to get the best estimate value for the lattice parameter corresponding to the minimum A free energy. For each run, a complete phonon calculation is performed at constant pressure and the free energy is recorded. At the end, the lattice parameters corresponding to the minimum free energy at dierent temperatures were v = For T = 283K, the lattice parameter is 4.11476 and the corresponding free energy is 15.4250542eV A For T = 293K, the lattice parameter is 4.11544 and the corresponding free energy is 15.4473226eV A by plugging these values in the thermal expansion coecient expression and performing numerical backward dierence dierentiation, the thermal expansion coecient, at T = 293K, which corresponds to a cell volume of 6.970257513 is A v = 4.95612 105 K 1 This value compares relatively well with the experimental value of 4.26 10 of the backward dierence mesh (10K steps). The relative error is 16.34%.
5

(2.2) K
1

given the crudeness

3
For the gold crystal, the lattice constant which minimizes the potential energy at zero pressure and zero temperature is 4.080076. at pressure p = 1atm, it is 4.080076 as well. A A Obviously, these lattice constants are much smaller than the ground state lattice constant calculated in problem 2. The reason for that is that although the two calculations are made at zero pressure, the

temperature for the calculation in problem 2 was 293K while it is 0K in this case. The increase in the temperature causes some thermal expansion which increases the lattice parameter. Another reason is that in the calculations of this problem, we are minimizing the potential energy of the system while in problem 2, we were looking for the most stable conguration which minimizes the free energy but not necessarily the potential energy. Since the free energy at zero temperature is just the enthalpy and that enthalpy at zero pressure is the internal energy, which is the potential energy, so the potential energy minimization carried out in this problem is a free energy minimization at the same time while this is not the case in problem 2. G = H T S = U + pV T S (3.1)

The total lattice enthalpy at p = 0atm is 15.11682514 and that at p = 1atm is 15.11678219eV . The relative dierence is less than 2.85 104 %. That minor dierence is highly negligible, which points out that the pressure is not signicant in these kinds of calculations.

4
The free energy curves at dierent temperatures, ranging from 0K to 1500K were generated for the 4 given structures and they are plotted below along with some details about the respective lattice. For the pure gold lattice, the lattice parameter is 4.08 in all three directions. The cell description, in A fractional coordinates, is Au 0.0000000 0.0000000 0.0000000 Au 0.0000000 0.5000000 0.5000000 Au 0.5000000 0.0000000 0.5000000 Au 0.5000000 0.5000000 0.0000000 For the pure Palladium lattice, the lattice parameter is 3.89 in all three directions. The cell description, A in fractional coordinates, is Pd 0.0000000 0.0000000 0.0000000 Pd 0.0000000 0.5000000 0.5000000 Pd 0.5000000 0.0000000 0.5000000 Pd 0.5000000 0.5000000 0.0000000 For the Au3 P d lattice in the L12 conguration, the lattice parameter is 4.08 in all three directions. A The cell description, in fractional coordinates, is Au 0.0000000 0.0000000 0.0000000 Au 0.0000000 0.5000000 0.5000000 Pd 0.5000000 0.0000000 0.5000000 Au 0.5000000 0.5000000 0.0000000 Finally, for the Au3 P d lattice in the DO22 conguration, the lattice parameter is 4.08 in the x and z A directions while it is 8.16 in the y direction. The cell description, in fractional coordinates, is Au Pd Au Au Pd Au Au Au 0.0000000 0.5000000 0.5000000 0.0000000 0.0000000 0.5000000 0.0000000 0.5000000 0.0000000 0.0000000 0.2500000 0.2500000 0.5000000 0.7500000 0.7500000 0.5000000 0.0000000 0.5000000 0.0000000 0.5000000 0.0000000 0.0000000 0.5000000 0.5000000

Figure 1: Free Energy vs Temperature A similar plot, but for the free energy per atom, is given below. Along with the previous curves, the free energy per atom for the separate Au and P d phases per atom is plotted as well for comparison purposes.

Figure 2: Free Energy vs Temperature per atom From the previous curves, the most stable phase is certainly the phase where gold and Palladium coexist 3

without forming Au3 P d since this phase has a lower free energy. This is true for the whole temperature range under study. The potential energies at zero temperature for the 4 structures are 15.11683 eV , 15.10158 eV , 11.51433 eV and 22.90194 eV respectively. These values, and hence, the dierences between them, are very close to the values for the free energies at the same temperature which is expected since there are no entropic eects at zero temperature.

5
The supplied input le was used to plot the dispersion relations for gold at zero temperature. The described primitive unit cell is used for the calculations. The path along which the dispersion relations are plotted is X W K L where these points are dened in the given Brillouin zone. The output gulp.disp gives the three frequencies for each K point along the chosen path. All the plots were concatenated to give the following plot

Each segment of the 5 segments has 30 K points. The coordinates in the reciprocal lattice vectors of the end points of each segment are given below. to X : 0.5 0.0 0.5 to 0.5 0.0 0.5 X to W : 0.5 0.0 0.5 to 0.5 0.25 0.75 W to K : 0.5 0.25 0.75 to 0.375 0.375 0.75 K to : 0.375 0.375 0.75 to 0.0 0.0 0.0 to L : 0.0 0.0 0.0 to 0.5 0.5 0.5 so that for each 30 K points in the given plot, the coordinates of a K point change linearly along the respective endpoints in the reciprocal space.