Introduction to Plane Waves and kpoints

Umesh V. Waghmare

Theoretical Sciences Unit J N C A S R Bangalore ICMR

OUTLINE
Periodic Systems Kohn-Sham wavefunctions of periodic systems

Representations of wavefunctions: Plane Waves

Consequences of symmetries Brillouin Zone Integrations Metallic Systems

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Examples:

Structure of periodic systems

Bravais Lattice: Periodicity periodic unit: unit cell vectors a1 , a2 , a3 Cell volume: cell Lattice points: R = n1a1 + n2a2 + n3a3

Basis: Structure within a unit positions and types of atoms: i, Zi

Surface (2D)

Wire (1D)

                                                                    

Crystal (3D)

Periodic Systems

Cluster (0D)

a2

a1

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Unit Cell and Choices

Unit Cell Basis

Na: Number of atoms per unit cell (basis) For unit cells 1 and 2, Na = 2. For unit cell 3, Na = 4.

Primitive unit cell: Na is the smallest All choices should give equivalent description

Reciprocal Space
Fourier Transfrom: f (r) f (q) Periodic Boundary Conditions: f (r) = f (r + Niai) Born von Karmen conditions: exp(iq Niai) = 1 q ai = 2 integer N
1
i

f (q) = crys crys drf (r)exp(iq r), crys = cell iNi

For a function with lattice periodicity: f (r) = f (r + R), q = m1b1 + m2b2 + m3b3 and bi aj = 2ij q=G bi: primitive vectors of reciprocal space lattice eg. b1 = 2a2 a3/cell G: reciprocal space lattice (RSL) vector

 Brillouin Zone (BZ): Wigner Seitz cell in RS, volume, BZ = (2)3/cell For a general function: q = k + G,
n n n k = N1 b1 + N2 b2 + N3 b3 1 2 3 k primitive cell of the RSL or BZ.

a1

b1 k

L1= N a1 Real Space

G max Reciprocal Space

FFT meshes: Long length-scales: Li = Ni|ai|, 1/k Short length-scales: r 1/Gmax

Periodic systems: Electron wavefunctions

Translational symmetry: TR H = H TR Bloch theorem: R(r) = (r + R) = exp(ik R)(r) k is a quantum number to label : k (r) = exp(ik r)uk (r)

uk (r + R) = uk (r) is lattice periodic.

For each k, discrete energy eigenvalues: form energy bands ik : non-analytic only at BZ-boundary ik Integrals in kspace (in DFT): (r) =
i BZ

dk|ik (r)|2

Representation of ik : Plane Waves

ik (r) = 1 exp(ik r) cell C G exp(iG r)
ik

1 Plane Waves: < r|G >= exp(iG r) cell

C G = cell < G|r > uik (r)dr ik Orthonormality: < G|G >= G,G No dependence on the basis of a crystal Computation of forces easy! A single parameter: Ecut G basis set, if 1 |G|2 < Ecut 2 Uniform resolution in direct space: 2 r G
cut

Plane Waves (contd)

Plane wave cuto for density: 2Gcut 4Ecut

G cut

Same cutoff, but lattice constant changed

Basis set depends on the lattice constant: Pulay corrections FFT essential for eciency (T + VKS ): eg. V (r)(r): convolution in G-space!

Symmetry
Time reversal symmetry: non-magnetic systems ik = ik Inversion symmetry: r r leads to real C G .
ik

Point symmetries S: SH = H S rotations, reections, inversions and combinations. also an eigenfunction with energy ik . Space Groups (230): combination of point and translational symmetries Irreducible representations (Irrep): point group of k: S Gk if S k = k Star of k: ki = S.k; Ns vectors. D(Irrep of the space group): D = Dirrepof Gk Ns i,S 1k (r) = i,k (Sr)

Symmetries (contd)
Irreducible BZ (IBZ): The smallest region in the BZ such that there are no two ks that belong to the same star.

Knowledge of wavefunctions in IBZ wavefunctions elsewhere in the BZ.

Band structure plots often are shown along the high symmetry lines.

Irrep labels at various ks determine the symmetry of localized Wannier functions.

BZ Integration: Special k-points

Accurate integration: BZ k f ( ki ) dkf (k) = Nk i BZ Symmetries: BZ replaced by IBZ A scalar property: eg. ik f (ki) = k IBZ wk f (ki) kiBZ i wk : weight of a k-point. Scalar eld: eg. density I (r) = k IBZ wk (ki, r)
1 (r) = N
i S

S I (Sr)

Special k-points
f (k) = f (R) exp(ik R)

f (R) decays o exponentially (insulators).

Baldereschi point: there is a mean value point (MVP) where the integrand equals the integral symmetries approx. location of MVP eg. SC: k = (/2a)(1, 1, 1) BCC: k = (2/a)(1, 1, 3)/6.

Chadi and Cohen schemes: Generalization of the MVP idea to get larger sets

Monkhorst-Pack k-points:
3

k(n1, n2, n3) =

2ni Ni 1 bi 2Ni i

 Uniform mesh; exact integration for Fourier components R up to Niai. Scaled reciprocal lattice with an oset. Ni = 2 for SC gives the Baldereschi point For cubic case, even Ni recommended: avoids high symmetry ks (eg. (000) and BZ boundaries)

See Moreno and Soler PRB 45, 13841 (92). Note: even Ni meshes do not satisfy BvK conditions.

Symmetry of MP k-point mesh

(1,1,0) (0,1,0)

(1,0,0)

Symmetry of the hexagonal lattice is broken by an even Ni Monkhorst-Pack mesh. However, a shift in this mesh restores its symmetry.

an odd Ni M-P mesh maintains the hexagonal symmetry.

k-point sampling: Metals

Presence of a Fermi surface: Discontinuities in occupation numbers fik : eg. BZ dk ik fik Smear or smoothen the occupation numbers: scale = = kB T Various schemes of smearing a delta function (x = F ): Fermi-Dirac smearing: 0.25/cosh2(x/2)
2 )/ Gaussian smearing: exp(x

f( )

Nk for convergence of Etot(Nk , ) increseas with small and band gap.

Co nv er e nc ge

Nk

kpoints: Practicalities
Supercell (Ns unit cells) calculations: Brillouin zone is smaller: Nk 1/Ns Number of PW is larger: Npw Ns Mapping for identical representation: ks + G s = k Perturbation calculations: perturbation with wave vector qp Ideally, for any k, k + qp {k} supercell commensurate with qp has equivalent set of kpoints.

How to choose cutos?

Ecut: Ref. Erics talk. Convergence of energy of a single atom. Energy dierences converge faster than absolute energies.

Ekinetic,q>qc < 0.001 Ekinetic Which properties? Stresses, elastic moduli need higher Ecut. Nk : large if band gap is small. small for at bands (eg. ionic insulators). Which properties? dielectric response: higher Nk (eg. Si).

Lab Exercise
Use multi-dataset inputs: Silicon, diamond structure (a=5.41 A): Use Ecut = 8 Ha, MP k-points (NNN), for N from 2 to 8 and plot Etot vs N . with no shift (oset). with a shift (oset), say 0.5 0.5 0.5. Aluminium, FCC structure (a=4.04 ): A Use Ecut = 8 Ha, MP k-points (NNN), for N from 4 to 12 and = kB T =0.02, 0.04, 0.08, 0.12, 0.16 eV. Plot Etot as a function of Nk . Plot Etot as a function of .

Summary
Plane wave cuto Ecut controls the smallest length-scale

kpoints control the longest length-scale kpoints applicable to electrons and phonons Various kpoint schemes for BZ sampling Number of k-points should increase with decreasing band gap and smearing T.

Use of symmetries allows treatment of only symmetry inequivalent kpoints and reduces computation.

References
A. Baldereschi, PRB 7, 5212 (1973). D. J. Chadi and M. L. Cohen, PRB 7, 692 (1973).

H. J. Monkhorst and J. D. Pack, PRB 13, 5897 (1976).

J. Moreno and J. M. Soler, PRB 45, 13891 (1992).

Symmetry in Physics I and II, by J. P. Elliott and P. G. Dawber.

Electronic Structure: Basic Theory and Practical Methods, Richard Martin.