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MD Project #1

1. Equilibrium Lattice Constant and Bulk Modulus


Silicon 1.1 Cohesive Energy
Under ambient condition silicon lattice prefers the diamond-cubic (DC) structure. In computer simulations, we create Si crystals with different structures, such as face-centered-cubic (FCC), body-centered-cubic (BCC), simple-cubic (SC) and so on. With a reasonable potential, we shall see the structure with the lowest ground state energy is diamond-cubic. In this section, we use LAMMPS to show this. The lattice energy and the number density are defined as

E pot N

N V

where Epot is the potential energy of the lattice, N is total number of atoms in the simulation cell with volume V . We choose the Stillinger-Weber (SW) potential model[1][2] and run LAMMPS. An example is given here. To calculate Epot as a function of lattice constant (DC), do
$ lmp < in.Silicon log dc.log

View the log file with


$ grep ^@ dc.log

In the input file in.Silicon, you may see

units atom_style variable 5.4314 5.4315 lattice #lattice #lattice #lattice #lattice region create_box create_atoms pair_style pair_coeff mass neighbor neigh_modify variable variable timestep thermo compute compute compute dump run print clear next jump

metal atomic x index 5.4305 5.4306 5.4307 5.4308 5.4309 5.4310 5.4311 5.4312 5.4313

diamond $x diamond 5.431 fcc 3.615 bcc 3.28 sc 2.60 box block 0 3 0 3 0 3 1 box 1 box sw * * Si.sw Si 1 28 1.0 bin every 1 delay 5 check yes P equal pe/216 r equal 216/($x*3)^3 0.005 10 3 all 4 all 5 all 1 all 0 "@@@@ pe/atom ke/atom coord/atom 3.0 custom 1 dump.atom id xs ys zs c_3 c_4 c_5 (lattice parameter, rho, energy per atom): $x $r $P"

x in.Silicon

From the log file, you find out that the number of atoms for the 3 3 3 DC cell is 216 ( 8 33 = 216 , eight atoms in a unit cell). For other structures, the number of atoms in a 3 3 3 cell is given in table 1. Table 1. Number of atoms in different crystal structures Crystal Structure SC BCC FCC DC No. of atoms in the unit cell 1 2 4 8 Total No. of atoms 27 54 108 216

The volume of the supercell is obtained from the determinant of the H matrix [3]

V = det(H ) = H(1,1)H(2, 2)H(3,3)


if H is a diagonal matrix (the same is true for an upper triangular matrix), i.e., V is the diagonal product of H. In LAMMPS, the unit of length is angstrom () so the unit of volume is 3.
2

For other crystal structures, the energy (in eV) as a function of (in 1/3) can be calculated in a similar way (Fig. 1). Clearly, the structure with the lowest ground state energy is DC. The equilibrium lattice constant (a0) can be determined from the () curve where is minimum (the cohesive energy Ecoh). For DC structure, one found a0 = 5.431 and Ecoh = 4.3365 eV (Fig. 2).

Fig.1 Ground state energy of Si with different lattice structures.

Fig.2 Energy as a function of lattice constant (DC-Si), fitted by the 5th-order polynomial:

E = 104799.57911+ 27112.82866a +15604.99601a2 7592.99351a3 +1134.25198a4 57.82091a5

1.2 Bulk Modulus


The calculated () curve can be used to determine the bulk modulus of a lattice. The bulk modulus (B) is dened as[4]

dP dV / V

where V is the volume of a cubic unit cell and P the pressure. The cohesive energy or binding energy (E) per atom we calculated is a function of the lattice parameter, a. For a cubic cell, the total energy is given by =ME, where M is the number of atoms in the unit cell the volume of which is given by V = a 3 . Pressure is given by

P=
and the bulk modulus

d M dE = 2 3a da dV
M d 2E 9a0 da 2

B=

a0

where a0 is the equilibrium lattice parameter corresponding to the minimum of E. From polynomial fitting one can easily get

d 2E da 2

, which is 3.87081 eV/ 2 in our


a0

case (Fig. 2). According to the equation above the calculated B is 101.4 GPa, comparing very well with B ~ 99 GPa measured in real experiments [2].

Notes
1. F. H. Stillinger and T. A. Weber, Phys. Rev. B 31, 5262 (1985). 2. H. Balamane, T. Halicioglu, and W. A. Tiler, Phys. Rev. B 46, 2250 (1992) 3. The matrix H is sued to define the size and the shape of a supercell.

H = [c1 c2 c3 ] , where ci 's are three periodicity vectors. In LAMMPS, the


matrix H becomes a diagonal matrix when a supercell is rectangular (after reorienting the coordinate system). 4. ZH Jin. Bulk Modulus of Si and Cu.

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