Quantum Matter / Matéria Quântica
Problem Set 1 — Lattice sums and Wannier states
Notation recap. Use aj to designate the primitive vectors of a Bravais lattice L, and bj for the
primitive vectors of the corresponding reciprocal lattice L̃. Hence, for R ∈ L or G ∈ L̃,
X
d X
d
R= nj aj (nj ∈ Z), G= mj bj (mj ∈ Z),
j=1 j=1
where d ∈ {1, 2, 3} is the spatial dimension of the crystalline system of interest. Denote the volumes
enclosed by the primitive cell in direct and reciprocal space as Ωc and Ω̃c , respectively, where
Ω̃c = (2π)d /Ωc ; use “FBZ” to designate the first Brillouin zone.
With periodic boundary conditions (PBC), the wavevector k that identifies each Bloch eigenstate
is quantized according to
X
d
sj
k= bj , sj = 0, 1, . . . , Ncj − 1,
Ncj
j=1
where Ncj is the (linear) number of unit cells along the primitive direction aj ; there are a total
Nc ≡ Nc1 × · · · × Ncd such k vectors, as many as the total number of unit cells in the crystal. The
total volume of the crystal, Ω, is therefore given by Ω = Nc Ωc .
Problem 1 (lattice sums)
Assuming a lattice with periodic boundary conditions and, hence, k to be quantized as indicated
above, demonstrate the following exact results:
a) For any wavevector k,
X
eik·R = Nc δk,0 , ∀ k ∈ FBZ.
R∈L
b) For any vector R of the Bravais lattice,
X
eik·R = Nc δR,0 , ∀ R ∈ L.
k ∈ FBZ
c) Use one of the results above to show that
1
ˆ
eik·r dr = δk,0 , ∀ k ∈ FBZ,
Ω Ω
where the integral is over the whole volume Ω occupied by the crystal.
1
Problem 2 (Wannier states)
Suppose we are given the complete set of exact Bloch eigenstates, |ψk,n i, that span the single-
particle Hilbert space of an electron in a crystal1 . We may build another complete set of states,
known as Wannier basis, where the Wannier state centered at lattice site R ∈ L and belonging to
band n is defined as
1 X
|wR,n i ≡ √ e−ik·R |ψk,n i, hψk,n |ψk′ ,n′ i = δk,k′ δn,n′ .
Nc k ∈ FBZ
The Wannier basis is well suited to describe local (atomic-scale) effects in a crystal. As an application
of the identities stated in Problem 1 above, establish the following properties of these |wR,n i.
a) Show that the inverse relation is given by
1 X ik·R
|ψk,n i ≡ √ e |wR,n i, k ∈ FBZ.
Nc R ∈ L
b) Wannier states centered at different lattice sites, or belonging to different bands, are exactly
orthogonal: hwR,n |wR′ ,n′ i = δR,R′ δn,n′ .
c) The wavefunction hr|wR,n i of a Wannier state is not a function of R and r independently,
but a function of the difference r − R only:
hr|wR,n i = hr − R|w0,n i ≡ wn (r − R).
d) The probability density for finding an electron in band n at position r ∈ Rd ∈ Ω is given by
X X
|ψk,n (r)|2 = |wn (r − R)|2 .
k ∈ FBZ R∈L
e) It can be generally shown that the Wannier wavefunction wn (r − R) is spatially localized
around R. In some particular cases, it is straightforward to demonstrate this property ex-
actly. For example, compute the Wannier wavefunction wn (r − R) for a 1D crystal with
lattice constant a, in the limit Nc → ∞, and assuming that the periodic part of the Bloch
wavefunctions are independent of k:
1 1
ψk,n (r) = √ eik·r uk,n (r) −→ ψk,n (r) = √ eik·r un (r),
Ω Ω
where Ω is the volume of the crystal and uk,n (r) is a lattice-periodic part: uk,n (r + R) =
uk,n (r). Show that wn (r − R) obtained in this case is manifestly localized around R.
1
In a frequent practical scenario, the Bloch states are obtained as the output of a numerical, first-principles, density-
functional theory calculation.
2
f) Consider the orthogonal tight-binding (TB) approximation to a single band of some crystal,
in which we expand the Bloch states in a linear combination of atomic orbitals φ(r) ≡ hr|φi,
1 X ik·R
|ψk i = √ e |Ri, hr|Ri = φ(r − R).
Nc R
Show that |wR,n i ≃ |Ri and interpret this result.
g) Generalize the previous result to the orthogonal TB approximation with an arbitrary number
of orbitals and bands, where we expand
X (α) 1
X
|ψkn i = bkn √ eik·R |R, αi, hr|R, αi = φ(α) (r − R − uα ),
α
Nc R
where uα is the position of orbital φ(α) relative to the origin of the unit cell. Approximating
(α) (α) (α)
bkn ≃ bn (i.e., we neglecting the k dependence of bkn ), obtain |wR,n i in terms of the local
TB basis {|R, αi}. Comment on the spatial extent of the Wannier state |wR,n i.
