effect at long and medium range in a conventional gradient corrected density functional by theC6·R−6term. In the literature it is shown how the introduction of dispersive forces works in realistic chemical applications reach results in an improved accuracy compared with the standard GGA methods.
2.3 Ab-Initio Simulation of Solids
This section introduces how DFT can be used to predict important physical properties of solids. Crystalline solids may be described asordered repetitions of atoms or group of atoms in three dimensions, with an infinite number of them.
Because of that huge amount of atoms, a reliableab-initioDFT treatment of the system seems to be an unaffordable task. However, crystals are structures with translational periodicity governed by the geometry195,196of arepeating motif.
2.3.1 Lattice Structure
Considering an ideal crystal, all repeating units are identical, which means that they are related by translational symmetry operations, corresponding to the set of vectors:
T(u,v,w)=u~a+v~b+w~c (2.12) Whereu,vandware three integers from−∞to∞, and~a,~b,~care non-coplanar vectors defining the basis of a three dimensional space. The set of points generated through all the translation vectorsT(u,v,w)forms a three-dimensional lattice where the points are calledlattice nodes.
The given integersu,v andwdefine a given vector, which provides the corre-sponding coordinates of the node in the reference system already defined by~a,~b and~c. The final parallelepiped defined by the three basis vectors is calledunit cell. The lattice constants are the three module a, b, c and three anglesα,β,γ between the vectors, as shown in the following figure. Several unit cells can be defined, where the smallest one is the so-calledprimitive cell.
48 Chapter 2 - Theoretical Background
O a
c
b α
β γ
Figure 2.1:Unit cell lattice constants (a,b,c) and (α,β,γ)
The periodic repetition of the "motif" inside the unit cell by an infinite set of vectors yields the crystal structure, which is set by the lattice constants and the coordinates (x,y,z) of all atoms in the unit cell. These coordinates are the components of the vectors:
ri =xia+yib+zic (i= 1,2· · ·N) (2.13) Expressing the atoms coordinates as fractions of the unit cell in each of the three directions (a,b,c) separated by the angles (α,β,γ) we set the so-calledfractional coordinates.
xf rac=x′/a yf rac=y′/b zf rac=z′/c (2.14) The reciprocal lattice is defined by three vectorsa′,b′andc′derived from thea,b andcvectors of the direct cell.
a′= 2πb×c
L3 b′ = 2πc×a
L3 c′= 2πa×b
L3 (2.15)
The reciprocal cell of a cubic cell with side lengthLis also a cube, with the side length2π/L. The equivalent of a unit cell in reciprocal space is called the first Brillouin Zone.
2.3 - Ab-Initio Simulation of Solids 49
2.3.2 Space Groups
In crystals a lot of symmetry operations may coexist, considering only the oper-ations which do not imply transloper-ations we get the so-calledpoint groupssince the operator form a mathematical group and leave one point fixed (rotations). In three dimensions, there are 32 possible crystallographic point groups. Then, it is convenient to group together the symmetry classes with common lattice fea-tures which are described by unit cells of the same type, seven different groups may be identified (triclinic, monoclinic, orthorhombic, tetragonal, rhombohedral, hexagonal and cubic) known as theseven crystal systems.
Each crystal system can be associated with a primitive cell compatible with the point groups that belong to that system. These primitive cells define a lattice type, but there are other types of lattices not based on the primitive cells. Overall, there are 14 possible space lattices, that are calledBravais latticeslisted in 1850.
For example, the tetragonal crystal system has two bravais lattice, the simple tetragonal and the body-centered tetragonal lattice, as shown in the following figure.
Figure 2.2:Bravais Lattices of the tetragonal crystal system
Space groups in three dimensions are made from the combination of the 32 crystallographic point groups with 14 Bravais lattices, each of them belonging to one of the 7 lattice systems, as a result the total number of possible combinations leads to 230 differentcrystallographic space groups. As a consequence of the presence of symmetry elements, symmetry-equivalent atoms or molecules will share the unit cell space.
50 Chapter 2 - Theoretical Background The smallest part of the unit cell is called theasymmetric unit, which is able to generate the whole cell contents when the symmetry operations of the space group are applied to them.
2.3.3 Crystallographic Planes
Crystalline solids are anisotropic being necessary to identify in a simple way planesin which specific physical properties can be observed. Crystal faces can thus be described by means of three indices that are whole numbers, and these, in fact, are always small whole numbers for naturally growing crystals. These three integers describing the orientation perpendicular to a plane are called Miller indices, and the symbolsh, k and l are used for them. We will restrict ourselves to planes where the indices of which are relatively prime numbers; that is, the indices have no common factors. Such restriction is logical in classical crystallography, since only the orientation of a crystal face has significance, and not how far it is from some arbitrarily defined origin.
Without loss of generality, the plane (hkl) can be described by the equation:
hx+ky+lz= 1 (2.16)
This equation has solutions wherex, y andz are integers, e.g., the following equation:
21x+ 10y+ 6z= 1 (2.17) It is satisfied by such points as (1,-2,0) or (3,-5,-2); that is, these points lie on the place (21, 10, 6). However, points for which the coordinates are integers are lattice points. Therefore, every plane (hkl) passes through a set of lattice points.
Since all lattice points are identical, planes identical in all respects, including orientation, must pass through all lattice points.
Crystallographic planes parallel to faces of the unit cell are of type (h,0,0), (0, k,0) and (0,0, l). Other planes such as the (111) shown in Figure 2.3 can also be defined.
2.3 - Ab-Initio Simulation of Solids 51
Figure 2.3:Crystallographic plane (1 1 1) into a unit cell
2.3.4 Periodic Boundary Conditions and Bloch’s Theorem
It is assumed that a crystalline solid is an infinite system (Figure 2.4), made of macroscopic finite crystals containingN =N1·N2·N3cells, whose sides are Njaj.
Figure 2.4:Periodic Boundary condion of a water molecule in a cell.
The finite crystal is part of an infinite system, which is delimited in a formal way, where the wavefunction obeys the followingBorn-Von Karmanperiodic boundary conditions.197
ψi,k(r+Njaj) =ψi,k(r) (2.18) whereψi,kmust satisfy the Bloch theorem:
ψi,k(r+Njaj) =ψi,k(r) =e(iNjk·aj)= 1 (2.19)
52 Chapter 2 - Theoretical Background The previous expression can be rewritten with the reciprocal lattice vector (a′,b′,c′), which results directly from the direct lattice and satisfy the relationai·bj= 2π·δik:
e(2πiNjkj)= 1 (2.20)
Wherekj = nj/Nj, andnj is any integer0 ≤ nj ≤Nj. In periodic boundary conditions the generalkvector inside theBrillouin Zoneis defined as:
k= n1
N1a′+ n2
N2b′+ n3
N3c′ (2.21)
Eachkpoint can be associated with a parallelepiped of volumevk
vk= (a′
N1)×( b′
N2)×( c′
N3) =VBZ
N (2.22)
whereVBZ is the volume of theBrillouin Zoneand N is the number of unit cells in the macroscopic finite crystal. For increasing values of N, the volume vk
progressively decreases, which means that the k-points get progressively closer until they cover the entireBrillouin Zonevolume as a continuous variable, for N approaching infinite.
The correlated nature of the electrons within a solid is not the only obstacle to solving the Schrödinger equation for condensed matter systems: for solids, one must also bear in mind the effectively infinite number of electrons within the solid.
One may appeal toBloch’s Theorem198 in order to solve this problem. Instead of being required to consider an infinite number of electrons, it is only necessary to consider the number of electrons within theunit cell