Statement of Bloch theorem: Bloch theorem states that, the solutions of Schrödinger wave equation for an electron

moving in a periodic potential are the plane waves modulated by a function having the same periodicity as that of the
lattice.
Explanation: For an electron moving in a one-dimensional periodic potential, 𝑉(𝑥), the Schrödinger equation is
written as
𝑑2 𝑦 2𝑚
+ ℏ2 [𝐸 − 𝑉(𝑥)] = 0-------------------------- (1)
𝑑𝑥 2
Where 𝑉(𝑥) = 𝑉(𝑥 + 𝑎) --------------------------- (2)
and a is lattice constant.
According to the Bloch theorem, the solution of the above equation must be of the form
𝜓(𝑥) = 𝑒 ±𝑖𝐾𝑥 𝑢𝐾 (𝑥) --------------------------- (3)
Where 𝑢𝐾 (𝑥) = 𝑢𝐾 (𝑥 + 𝑎)------------------ (4)
K=wave vector. 𝑢𝐾 is a function having complete periodicity of the lattice.
The functions of the type of equation (3) are known as Block function
For three dimensional case it is given as 𝜓(𝑟⃗) = 𝑒 ±𝑖𝐾⃗⃗∙𝑟⃗ 𝑢𝐾 (𝑟⃗)
Proof:Let 𝑔(𝑥) and 𝑓(𝑥) be two real and independent solutions of the second order differential equation (1).
So the general solution can be written as
𝜓(𝑥) = 𝐴 𝑓(𝑥) + 𝐵 𝑔(𝑥) ------------------ (5)
Since 𝑉(𝑥) = 𝑉(𝑥 + 𝑎), the functions 𝑓(𝑥 + 𝑎) and 𝑔(𝑥 + 𝑎) must also be the solutions of equation (1). But only
two independent solutions are possible for second order linear differential equation. So 𝑓(𝑥 + 𝑎) and 𝑔(𝑥 + 𝑎) must
be expressed as a linear combination of 𝑓(𝑥) and 𝑔(𝑥) as
𝑓(𝑥 + 𝑎) = 𝛼1 𝑓(𝑥) + 𝛼2 𝑔(𝑥) ∙∙∙∙∙∙∙∙ (𝑎)
} --- (6)
𝑔(𝑥 + 𝑎) = 𝛽1 𝑓(𝑥) + 𝛽2 𝑔(𝑥) ∙∙∙∙∙∙∙∙ (𝑏)
Where 𝛼1 , 𝛼2 , 𝛽1 and 𝛽2 are the real functions of energy E.
Now we may write another solution from equation (5) using equation (6) as
𝜓(𝑥 + 𝑎) = 𝐴 𝑓(𝑥 + 𝑎) + 𝐵 𝑔(𝑥 + 𝑎)
= (𝐴𝛼1 + 𝐵𝛽1 )𝑓(𝑥) + (𝐴𝛼2 + 𝐵𝛽2 )𝑔(𝑥) --- (7) the property given in equation (6) we should choose 𝐴 and 𝐵 such
that
𝐴𝛼1 + 𝐵𝛽1 = 𝜆𝐴 ∙∙∙∙∙∙∙∙ (𝑎)
} ------ (8)
𝐴𝛼2 + 𝐵𝛽2 = 𝜆𝐵 ∙∙∙∙∙∙∙∙∙ (𝑏)
Where 𝜆 is a constant.
So equation (7) may be written as
𝜓(𝑥 + 𝑎) = 𝜆[𝐴𝑓(𝑥) + 𝐵𝑔(𝑥)] = 𝜆𝜓(𝑥) ----- (9)
The equations (8) has non-zero values of 𝐴 and 𝐵 only if the determinant of their co-efficient vanish.
𝛼 −𝜆 𝛽1
So | 1 |=0
𝛼2 𝛽2 − 𝜆
⇒ (𝛼1 − 𝜆)(𝛽2 − 𝜆) − 𝛼2 𝛽1 = 0
⇒ 𝛼1 𝛽2 − (𝛼1 + 𝛽2 )𝜆 + 𝜆2 − 𝛼2 𝛽1 = 0 ---- (10)
Taking first order derivative of equations (6) we get
𝑓′(𝑥 + 𝑎) = 𝛼1 𝑓′(𝑥) + 𝛼2 𝑔′(𝑥)
𝑔′(𝑥 + 𝑎) = 𝛽1 𝑓′(𝑥) + 𝛽2 𝑔′(𝑥)
Now, 𝑓(𝑥 + 𝑎) 𝑔′(𝑥 + 𝑎) – 𝑔(𝑥 + 𝑎) 𝑓′(𝑥 + 𝑎)
= [𝛼1 𝑓(𝑥) + 𝛼2 𝑔(𝑥)][𝛽1 𝑓′(𝑥) + 𝛽2 𝑔′(𝑥) ] − [𝛽1 𝑓(𝑥) + 𝛽2 𝑔(𝑥)][𝛼1 𝑓′(𝑥) + 𝛼2 𝑔′(𝑥)]
= 𝛼1 𝛽1 𝑓(𝑥)𝑓′(𝑥) + 𝛼1 𝛽2 𝑓(𝑥)𝑔′(𝑥) + 𝛼2 𝛽1 𝑔(𝑥)𝑓′(𝑥) + 𝛼2 𝛽2 𝑔(𝑥)𝑔′(𝑥)
−𝛼1 𝛽1 𝑓(𝑥)𝑓 ′ (𝑥) − 𝛼2 𝛽1 𝑓(𝑥)𝑔′ (𝑥) − 𝛼1 𝛽2 𝑔(𝑥)𝑓 ′ (𝑥) − 𝛼2 𝛽2 𝑔(𝑥)𝑔′(𝑥)
= [𝑓(𝑥)𝑔′(𝑥) − 𝑔(𝑥)𝑓′(𝑥)](𝛼1 𝛽2 − 𝛼2 𝛽1 ) ------ (11)
Due to periodic property we may write
𝑓(𝑥 + 𝑎) 𝑔′(𝑥 + 𝑎) – 𝑔(𝑥 + 𝑎) 𝑓′(𝑥 + 𝑎) = 𝑓(𝑥) 𝑔′(𝑥) – 𝑔(𝑥) 𝑓′(𝑥)
Putting this value in equation (11) we get
𝑓(𝑥) 𝑔′(𝑥) – 𝑔(𝑥) 𝑓′(𝑥) = [𝑓(𝑥)𝑔′(𝑥) − 𝑔(𝑥)𝑓′(𝑥)](𝛼1 𝛽1 − 𝛼2 𝛽1 )
⇒ (𝛼2 𝛽1 − 𝛼2 𝛽1 ) = 1
Putting this value in equation (10) we get
𝜆2 − (𝛼1 + 𝛽2 )𝜆 + 1 = 0
(𝛼 +𝛽 )±√(𝛼 +𝛽 )2 −4
⇒𝜆= 1 2 21 2
It gives two possible values 𝜆1 and 𝜆2 of 𝜆 such that 𝜆1 𝜆2 = 1. Thus there are two functions 𝜓1 (𝑥) and 𝜓2 (𝑥) which
satisfy equation (9).
Now we consider the following two cases
Case 1:For energy range in which (𝛼1 + 𝛽2 )2 > 4
In this case the roots of 𝜆 are real and reciprocal of each other. Their solutions do not represent a wave function and
thus there are no electronic state in the energy region corresponding to 𝜆1 and 𝜆2 .
Case 2:For energy range in which (𝛼1 + 𝛽2 )2 < 4
In this case the roots of 𝜆 are complex. 𝜆1 𝜆2 = 1 show that the roots will be complex to each other.. so we write 𝜆1 =
𝑒 𝑖𝐾𝑎 and 𝜆2 = 𝑒 −𝑖𝐾𝑎
Where K is real.
The corresponding wave functions 𝜓1 (𝑥) and 𝜓2 (𝑥) then have the property
𝜓1 (𝑥 + 𝑎) = 𝑒 𝑖𝐾𝑎 𝜓1 (𝑥)
𝜓2 (𝑥 + 𝑎) = 𝑒 −𝑖𝐾𝑎 𝜓2 (𝑥)
In general we write
𝜓 (𝑥 + 𝑎) = 𝑒 ±𝑖𝐾𝑎 𝜓 (𝑥) ------------------- (12)
Now we replace (𝑥) by (𝑥 + 𝑎) in equation (3) and get
𝜓(𝑥 + 𝑎) = 𝑒 ±𝑖𝐾(𝑥+𝑎) 𝑢𝐾 (𝑥 + 𝑎)
Using equation (4) it becomes 𝜓(𝑥 + 𝑎) = 𝑒 ±𝑖𝐾𝑎 𝑒 ±𝑖𝐾𝑥 𝑢𝐾 (𝑥)
⇒ 𝜓(𝑥 + 𝑎) = 𝑒 ±𝑖𝐾𝑎 𝜓(𝑥) ------------------- (13)
Equations (12) and (13) are the same.
Hence Bloch Theorem is proved.
Conclusion: From the above result it is clear that the energy spectrum of an electron in a periodic potential consists of
allowed and forbidden energy bands. The regions corresponding to complex values of 𝜆 represent the allowed energy
bands. The regions corresponding to real values of 𝜆 represent ther forbidden energy bands.
In three dimensions the Bloch Theorem is expressed as
𝜓𝑘 (𝑟⃗) = 𝑒 𝑖𝑘⃗⃗.𝑟⃗ 𝑢𝑘 (𝑟⃗)
Significance wave vector 𝒌 ⃗⃗: the wave vector 𝒌 ⃗⃗ has several properties
1. Under a crystal lattice translation which carries 𝑟⃗ to 𝑟⃗ + 𝑇 ⃗⃗ we have
⃗⃗ ⃗⃗ ⃗⃗ ⃗⃗) = 𝑒 𝑖𝑘⃗⃗.𝑇⃗⃗ 𝜓𝑘 (𝑟⃗)
⃗⃗) = 𝑒 𝑖𝑘.𝑇 𝑒 𝑖𝑘.𝑟⃗ 𝑢𝑘 (𝑟⃗ + 𝑇
𝜓𝑘 (𝑟⃗ + 𝑇
Because 𝑢𝑘 (𝑟⃗ + 𝑇⃗⃗) = 𝑢𝑘 (𝑟⃗).Thus 𝑒 𝑖𝑘⃗⃗.𝑇⃗⃗ is the phase factor by which a block function is multiplied when a crystal
⃗⃗ is made.
translation 𝑇
2. The quantity 𝑘 ⃗⃗ enters in the conservation laws that govern collision processes in crystal.