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How to justify unit cell normalization of Bloch functions?

Physics Asked by TeneT on March 16, 2021

As is widely known, non-square-integrable wavefunctions don’t belong to the Hilbert space, and therefore cannot represent physical states.

This is the case for e.g. oscillating wavefunctions and generally wavefunctions that do not vanish sufficiently rapidly at infinity (see however Normalizable wavefunction that does not vanish at infinity for counterexamples).

A particular example of such functions are Bloch waves, arising in solid state physics whenever we have a crystal lattice (and therefore a periodic potential). These are wavefunctions of the form (in one dimension)

$$psi_k(x) = u_k(x) e^{ikx}$$

where $u_k(x)$ is a periodic complex-valued function with the same periodicity as the lattice. Such wavefunctions are clearly non-normalizable over the whole space since

$$int_{- infty}^{+ infty} |psi_k(x)|^2 dx = int_{- infty}^{+ infty} |u_k(x)|^2 dx $$

and $|u_k(x)|^2$ is periodical.

Since we want to be able to calculate expectation values, a typical approach in solid state physics is to normalize this kind of functions not over the whole space, but only over the unit cell of the lattice. This in one dimension corresponds to writing the normalization condition as

$$ int_{0}^{a} |psi_k(x)|^2 dx = 1 $$

where $a$ is the cell parameter.

This surely allows to normalize the wavefunction, and to carry on calculations, but isn’t equivalent to saying that we are sure to find the electron inside a particular unit cell, at every time?

How is such a procedure justified from a physical point of view?

One Answer

I think that normalizing on a single cell does not mean that

we are sure to find the electron inside a particular unit cell

I think is just a way of simplifying calculation exploiting the fact that for certain periodic potential it doesn't matter on how many cells our wave function is defined on, any domain you choose yield the same expectation value.

Here I give a plausibility argument of this.

Think of the Bloch wave defined on the whole space, of the shape $psi_k(r)=exp(ikr)u_k(r)$, with u_k periodic with periodicity $a$, the same of the lattice.

Now slice it, so that you have one piece per cell.

Take one cell, normalize the piece of function to that cell:

$$begin{eqnarray} 1 &=& int_{0}^{a} psi_k(r)^{*}psi_k(r) &=& int_{0}^{a} exp(-ikr)u_k(r)^{*}exp(ikr)u_k(r) &=&int_{0}^{a} u_k(r)^{*}u_k(r) end{eqnarray}$$

Now let V a periodic potential with the same periodicity of the lattice and that $$V(r)exp(pm ikr)u_k(r)=exp(pm ikr)V(r) u_k(r)$$

The expectation value of V over the single cell is:

$$begin{eqnarray} int_{0}^{a} psi_k(r)^{*}V(r)psi_k(r)&=& int_{0}^{a} exp(-ikr)u_k(r)^{*}V(r)exp(ikr)u_k(r) &=&int_{0}^{a} u_k(r)^{*}V(r)u_k(r) end{eqnarray}$$

Now take, say 5, different cells at random, and consider the wave function on this domain, we normalize it so that

$$ sum_{i=1}^{5} int_{x_i}^{x_i+a} psi^{i}_{k}(r)^{*}psi^{i}_{k}(r) = 1 $$

where $x_i$ are lattice points. Due to the periodicity we are summing 5 copies of the same value so that each integral is: $$begin{eqnarray} int_{x_i}^{x_i+a} psi^{i}_{k}(r)^{*}psi^{i}_{k}(r)(r) &=& frac{1}{5} &=&int_{x_i}^{x_i+a} u^{i}_k(r)^{*}u^{i}_k(r) end{eqnarray}$$

then $u_k(r+x_i)=sqrt(5)*u^{i}_k(r)$ (since $u_k$ and $u^{i}_k$ are slices of the same function (which is periodic) apart from a normalization constant).

when we calculate the expected value of V we get: $$begin{eqnarray} sum_{i=1}^{5} int_{x_i}^{x_i+a} psi^{i}_{k}(r)^{*}V(r)psi^{i}_{k}(r) &=& &=& sum_{i=1}^{5} int_{x_i}^{x_i+a} exp(-ikr)u^{i}_k(r)^{*}V(r)exp(ikr)u^{i}_k(r) &=& 5*int_{x_i}^{x_i+a} u^{i}_k(r)^{*}V(r)u^{i}_k(r) &=& int_{x_i}^{x_i+a} u_k(r+x_i)^{*}V(r)u_k(r+x_i)dr &=& int_{0}^{a} u_k(y)^{*}V(r)u_k(y)dy end{eqnarray}$$

Which is the same expectation value we had obtained when normalizing on a single cell.

Answered by Muccagelato on March 16, 2021

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