Unit 1 : Approximation Methods

The WKB Method : one dimensional case

* Schrodinger equation is used for such potential systems or

particles that give an exact solution. Such as

particle in 1D box, SHO, H-atom

they are idealized systems → give exact solutions

* But there are many such systems in QM in which we do not

get exact solution. So Approximation Method is used.

*✔ The WKB Method is used to find the energy eigenvalue

and wavefunction of those systems for which the

classical limit is valid.

*✔ If there is a potential system in which the potential is

slowly varying. WKB approx requires that the variation

in the potential to be short compared to the

de-Broglie wavelength λ of the particle.

*✔ even though the potential is varying, the variation should

be so low & slow that it remains constant for the particle

de Broglie wavelength region.

*✔ This method discovered by Wentzel, Kramers & Brillouin.

& some contribution by Jeffrey → called JWKB approx.

2 ∂2 ψ
* -ħLet's assume an+E Vψ = particle
energy Eψ moving in the V potential region.
2
2m ∂x
∂²ψ / ∂x² + (2m/ħ²)(E - V)ψ = 0
2m(E - V) / ħ² = K² → K = Quantum Momentum

If E > V :
∂²ψ/∂x² + K²ψ = 0
Solution of the equation :
±iKx
ψ = Ae

+ sign → right side travelling wave

− sign → left side travelling wave

It is an oscillatory sinusoidal wavefunction.

Wavelength : K = 2π / λ
λ = 2π / K
Amplitude ⇒ A

If E < V :
∂²ψ/∂x² − K²ψ = 0
Solution of the equation :
±Kx
ψ = Ae

V ≠ constant but varying with position

V variation < λ
varying V → slowly ψ does not change

⇒ λ & A varying slowly

If E = V :
2m[V - E] / ħ² = K² = 0
λ = 2π / K = ∞

The classical Turning point is the point where the

classical particle reverses the direction of its Motion.

Solve the Schrodinger Equation

If the particle's energy is E and moving in the V potential region :

−ħ² ∂²ψ / 2m ∂x² + Vψ = Eψ

∂²ψ / ∂x² = − (2m/ħ²) [E−V] ψ

2m[E−V] = p² (classical Momentum)

∂²ψ/∂x² = −p²ψ/ħ² ⇒ ∂²ψ/∂x² + p²ψ/ħ² = 0

K² = p²/ħ² ⇒ K = p/ħ
p = Kħ = ħK
classical momentum of the particle = ħ × quantum momentum

iφ(x)
In the WKB approach, ψ = A e
iφ(x)
for only one direction : ψ = A e
iφx
Plane wave Ae Const. Momentum
iφ
WKB Ae Varying Momentum

iφ iφ
∂ψ/∂x = A e · iφ' + e A'
iφ
∂ψ/∂x = [A' + iAφ'] e

iφ
∂²ψ/∂x² = [A'' + 2iφ'A' + iAφ'' − A(φ')²] e

Real equation :
A'' − A(φ')² = −p² A / ħ²

Imaginary equation :

2A'φ' + Aφ'' = 0
Multiply by A :

2AA'φ' + A²φ'' = 0
(A² φ')' = 0
A² φ' = B²
A = B / √φ'
Since A'' ≪ (φ')², p²/ħ² (A varies slowly) ⇒ A'' ≈ 0

(φ')² = p²/ħ² ⇒ φ' = ±p/ħ

φ = ± (1/ħ) ∫ p dx

A = B / √φ' = B / √(p/ħ) = (B √ħ) / √P

A = C / √P

WKB Approximate solution :

±(i/ħ)∫pdx
ψ ≈ (C/√P) e

|ψ|² = ψ ψ* = C²/P ⇒ |ψ|² ∝ 1/P

|ψ|² = C² / (mv)

The higher the momentum, the less time the particle

will spend in that region & vice versa.

A Turning point is where E = V(x)

At this point K(x) = 0
WKB approx breaks down

particle changes from oscillatory → exponential behaviour.

WKB Approximate Solution :

Allowed region [E > V] :

(i/ħ)∫pdx −(i/ħ)∫pdx
ψ = (1/√P) [ A e + Be ]

Forbidden Region [E < V] :

−(1/ħ)∫pdx (1/ħ)∫pdx
ψ = (1/√P) [ C e + De ]
Tunneling Effect using WKB

V(x)

x₁ x₂

* Consider the motion of a particle of momentum p₀ = √(2mE)

incident on to potential Barrier

V(x) is slowly varying function of position x

* fig shows an energy E that is smaller than the

potential's maximum value Vₘ

* classically, the particle can't penetrate.

Region Wave Functions

ip₀x/ħ
incident wave : ψᵢ = A e

K = p₀/ħ
ip₀x/ħ
ψᵢ = A e
−ip₀x/ħ
reflected wave : ψᵣ = B e
ip₀x/ħ −ip₀x/ħ
ψ₁ = ψᵢ + ψᵣ = A e + Be
 ip₀x/ħ −ip₀x/ħ
ψ₁ = A e + Be

∂²ψ/∂x² + (2m/ħ²)(E−V)ψ = 0

K² = 2m(E−V) / ħ²

Region (3) wave function :

ip₀x/ħ −ip₀x/ħ
ψ₃ = E e + Fe [F = 0]
ip₀x/ħ
ψ₃ = E e Transmitted

Transmission Coefficient
T = |E|² / |A|² = (E/A)²

The wave function in the classically forbidden region [E < V(x)]

is given by WKB Method :

−(1/ħ)∫ˣˣˣ Pdx (1/ħ)∫Pdx
ψ₂ = (C/√P) e + (D/√P) e
where P(x) = i√[2m(V−E)]
[D ≈ 0] exponentially decreasing term

−(1/ħ)∫ Pdx
ψ₂ = (C/√P) e

Transmission Coefficient (Final)

γ = (1/ħ) ∫ˣˣ √[2m(V−E)] dx

−2γ
T ≈ e
 6. What is the Validity of WKB Approximation Method?

Ans: The WKB approximation is valid when the potential V(x)

changes slowly over the particle's wavelength.

| dλ(x) / dx | << 1

The Connection Formulas

V(x)

Classical region Tₚ Non classical region

E

* In the WKB approximation we have. But very close to the

turning point, any smooth function behaves like a straight line.

V(x) = V'(0) x + E

The Airy function :

∂²y/∂x² − xy = 0

ψₚ(x) = a·Ai(αx) + b·Bi(αx)

4. Eigen Energy: Potential Well with Two Vertical Walls
using WKB Approximation Method

V(x) = { some specified function 0<x<a

{ ∞ otherwise (x ≤ 0, x ≥ a)

Inside the well (E > V(x)) we have :

ψ(x) = (1/√P) [ C cosφ(x) + D sinφ(x) ]

φ(x) = (1/ħ) ∫₀ˣ P(x)dx

At x = 0 :

φ(0) = 0 ⇒ ψ(0) = C/√P

When C = 0 ⇒ ψ(0) = 0 ✓

At x = a :

ψ(a) = (1/√P) [D sin(φ(a))] = 0

sin(φ(a)) = 0
φ(a) = sin⁻¹(0) = nπ

nπ = (1/ħ) ∫₀ᵃ P(x) dx

∫₀ᵃ P(x) dx = nπħ [P(x) = √(2mE)]

∫₀ᵃ √(2mE) dx = nπħ

√(2mE) · a = nπħ

2mE = n²π²ħ² / a²
E = n² h² / 8ma²
7. Variational Principle & Variational Theorem

Ans: The variational principle is one of the most powerful

approximation methods in quantum mechanics.

It is mainly used to estimate the Ground state energy of a

system when an exact solution of Schrodinger equation is

difficult or impossible.

Hψ = Eψ
Eᵍ ≤ ⟨ψᵀ | H | ψᵀ⟩

ψᵀ = Σ Cₙψₙ → orthonormal set

⟨Σ Cₘψₘ | H | Σ Cₙψₙ⟩ = Eₙ Σ |Cₙ|²

Eᵍ ≤ Eₙ

Eₙ = ∫φ* Ĥ φ dτ / ∫φ*φ dτ ≥ Eᵍ

8. Estimate Ground State Energy of 1D SHO

using Variational Method

H = −ħ² ∂²ψ/2m ∂x² + ½mω²x²

Trial function → the Gaussian:

−bx²
ψ(x) = A e

b is constant. Normalize the wave function :

∫₋∞⁺∞ |ψ|² dx = 1
−2bx²
A² ∫₋∞⁺∞ e dx = 1
−cx²
using ∫₋∞⁺∞ e dx = √(π/c)
A = (2b/π)¼
 H = T + V

⟨T⟩ = ħ² b / 2m

⟨V⟩ = mω² / 8b

⟨H⟩ = ħ²b/2m + mω²/8b

For GS: minimize ⟨H⟩ w.r.t. b

d⟨H⟩/db = 0 ⇒ b = mω / 2ħ

⟨H⟩ = ħ²/2m · mω/2ħ + mω²/8 · 2ħ/mω

= ħω/4 + ħω/4

H ₘᵢₙ = ħω / 2

This matches the exact QM ground state energy!

Time-Independent Non-Degenerate Perturbation Theory

* Perturbation means introducing a small disturbance or

correction to a system whose exact solution is already known.

* H = H₀ + λH'
• H : Total Hamiltonian of the system

• H₀ : unperturbed Hamiltonian

• H' : perturbation (small additional effect)

• λ : small parameter to track how small the perturbation is.

First Order Perturbation

Hψₙ = Eₙψₙ

H = H₀ + λH' + λ²H'' + ...

ψₙ = ψ⁰ₙ + λψ¹ₙ + λ²ψ²ₙ + ...
Eₙ = E⁰ₙ + λE¹ₙ + λ²E²ₙ + ...

λ⁰ : H₀ψ⁰ₙ = E⁰ₙ ψ⁰ₙ

λ¹ : H₀ψ¹ₙ + H'ψ⁰ₙ = E⁰ₙψ¹ₙ + E¹ₙψ⁰ₙ

λ² : H₀ψ²ₙ + H'ψ¹ₙ = E⁰ₙψ²ₙ + E¹ₙψ¹ₙ + E²ₙψ⁰ₙ

For λ¹ :

H₀ψ¹ₙ + H'ψ⁰ₙ = E⁰ₙψ¹ₙ + E¹ₙψ⁰ₙ

× ⟨ψ⁰ₙ|

⟨ψ⁰ₙ|H₀|ψ¹ₙ⟩ + ⟨ψ⁰ₙ|H'|ψ⁰ₙ⟩ = E⁰ₙ⟨ψ⁰ₙ|ψ¹ₙ⟩ + E¹ₙ

E¹ₙ = ψ⁰ₙ | H' | ψ⁰ₙ

First order wave function correction :

ψ¹ₙ = Σ [ ⟨ψ⁰ₘ|H'|ψ⁰ₙ⟩ / (E⁰ₙ − E⁰ₘ) ] ψ⁰ₘ
m≠n
The Ground State of Helium

* The Helium atom consists of 2 electrons in orbit

around a nucleus containing two protons.

V₁ = −2e² / 4πε₀r₁ (potential btw +2e & -e₁)

V₂ = −2e² / 4πε₀r₂ (potential btw +2e & -e₂)

Vₑₑ = e² / 4πε₀|r₁−r₂| (e-e repulsion)

Total potential :

Vᵀ = −2e²/4πε₀r₁ − 2e²/4πε₀r₂ + e²/4πε₀|r₁−r₂|

H = −ħ²/2m(∇₁²+∇₂²) − e²/4πε₀(2/r₁ + 2/r₂ − 1/|r₁−r₂|)

Eᵍₛ = −78.975 eV (Experimental)

Zero-order unperturbed wave function :

−2(r₁+r₂)/a
ψ₁₀₀(r₁,r₂) = (8/πa³) e

Eₙ = 4E₁/n² ⇒ Eᵍ = 4E₁ = −4×13.6 = −54.4 eV

First order correction :

⟨Vₑₑ⟩ = 34 eV

Eᵍ = ⟨H⟩ = 8E₁ + ⟨Vₑₑ⟩

= 8 × (−13.6) + 34

= −108.8 eV + 34 eV
H = −74.8 eV