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Stark effect

Test - III
Course name : Atomic & Molecular Physics
Course code : PH-553

Presented by :
Lakhyajyoti Das (PHI14008)
Priyankush Ghosh (PHY17010)
Shamik Datta (PHY17002)
Department of Physics
Tezpur University
Outline :
• Introduction

• Linear Stark effect

• Quadratic Stark effect

• Conclusion

• References
Introduction
 The Stark effect is the shifting and splitting of spectral lines of atoms and molecules due to the
presence of an external electric field.

• The effect is named after the German physicist Johannes Stark, who discovered it in 1913.

• Independently discovered in the same year by the Italian physicist Antonino Lo Surdo, and in Italy
it is thus sometimes called the Stark–Lo Surdo effect.

• The discovery of this effect contributed importantly to the development of quantum theory and
was rewarded with the Nobel Prize in Physics for Johannes Stark in the year 1919.
Interaction energy due to presence of electric field,

𝐻 ′ = −𝑝Ԧ ⋅ 𝜀Ԧ = −𝑒𝜀0 𝑟 cos 𝜃

The total Hamiltonian is

𝑝 2 𝑒 2
𝐻 = 𝐻0 + 𝐻 ′ = − − 𝑒𝜀0 𝑟 cos 𝜃
2𝑚 𝑟
Solving the Schrodinger equation, we get

Ψ𝑛𝑙𝑚 = 𝑅𝑛𝑙 𝑟 𝑌𝑙𝑚 (𝜃, 𝜙)

The degeneracy for the nth excited state is


𝑛−1

𝑑 = ෍ 2𝑙 + 1 = 𝑛2 𝜀Ԧ = 𝜀0 𝑧Ƹ
𝑙=0

So, for the first excited state, 𝑑 = 22 = 4 ⟶ Four-fold degenerate

The states are (2 0 0), (2 1 0), (2 1 -1) and (2 1 1).


The first order Stark effect for ground state of H-atom:
For ground state, 𝑛 = 1,

Ψ100 = 𝑅10 𝑟 𝑌00 (𝜃, 𝜙)

3
1 2 𝑟
−𝑎
𝑅10 𝑟 =2 𝑒 0
𝑎0

The first order energy correction term is

1 0 0
𝐸𝑛 = 𝜓100 𝐻′ 𝜓100 = 0

• Therefore, there is no first order correction in the energy due to Stark effect.
Linear Stark effect
• Weak field effect

• Energy shift, Δ𝐸 ∝ Electric field 𝜀0

For 𝑛 = 2 we have four-fold degeneracy


𝑢1 ⟶ 𝑅20 𝑌00 = 𝑓(𝑟)
𝑢2 ⟶ 𝑅21 𝑌10 = 𝑐1 𝑔 𝑟 cos 𝜃
𝑢3 ⟶ 𝑅21 𝑌11 = 𝑐2 𝑔 𝑟 sin 𝜃 𝑒 𝑖𝜙
𝑢4 ⟶ 𝑅21 𝑌1−1 = 𝑐3 𝑔 𝑟 sin 𝜃 𝑒 −𝑖𝜙

First order correction term in energy can be obtained from 𝐸𝑛1 − 𝐻𝑛𝑚
′ =0

′ ′ ′ ′
𝐸𝑛′ − 𝐻11 𝐻12 𝐻13 𝐻14
′ ′ ′ ′
𝐻21 𝐸𝑛′ − 𝐻22 𝐻23 𝐻24
′ ′ ′ ′ =0
𝐻31 𝐻32 𝐸𝑛′ − 𝐻33 𝐻34
′ ′ ′ ′
𝐻41 𝐻41 𝐻43 𝐸𝑛′ − 𝐻44
Now

𝐸𝑛1 𝐻12 0 0

𝐻12 𝐸𝑛1 0 0
=0
0 0 𝐸𝑛1 0
0 0 0 𝐸𝑛1

Solving the determinant, we get


𝐸𝑛11 = −3𝑒𝜀0 𝑎0 , 𝐸𝑛12 = 3𝑒𝜀0 𝑎0
𝐸𝑛13 = 𝐸𝑛14 = 0

+3𝑒𝜀0 𝑎0

𝐸 = −3.4𝑒𝑉
−3𝑒𝜀0 𝑎0
Quadratic Stark effect
Performing the second order perturbation to the ground state,

< 𝜓100 |𝐻′ |𝜓𝑛𝑙𝑚 >< 𝜓𝑛𝑙𝑚 |𝐻′ |𝜓100 >


𝐸𝑛2 = ෍ 0 0
𝐸100 − 𝐸𝑛𝑙𝑚
𝑛𝑙𝑚≠100

< 𝜓𝑛𝑙𝑚 𝐻′ |𝜓100 > |2


= ෍ 0 0
𝐸100 − 𝐸𝑛𝑙𝑚
𝑛𝑙𝑚≠100

Ƹ 100 > |2
< 𝜓𝑛𝑙𝑚 𝑧|𝜓
= 𝑒2 𝜀0 2 ෍ 0 0
𝐸100 − 𝐸𝑛𝑙𝑚
𝑛𝑙𝑚≠100

3𝑒 4 𝑎0 2
=− 𝜀0
8

Thus, we can say that the shift in the energy value is

Δ𝐸 ∝ 𝜀0 2
Schematic diagram of Quadratic Stark effect

S orbit and 𝑙 = 0
Energy level Direction of electric field

∆𝐸 ∝ 𝜀0 2

𝜀0 = 0 𝜀0 ≠ 0
Conclusion:
• The linear Stark effect exhibits large, nearly symmetrical patterns. The interpretation of the linear Stark
effect was one of the first successes of the quantum theory.

• The quadratic Stark effect is basic to the explanation of the formation of molecules from atoms, of
dielectric constants, and of the broadening of spectral lines.

• The intermolecular Stark effect is produced by the action of the electric field from surrounding atoms or
ions on the emitting atom. The intermolecular effect causes a shifting and broadening of spectrum
lines. The molecules being in motion, these fields are inhomogeneous in space and also in time.
References:

• P. S. Epstein, The Stark Effect from the Point of View of Schroedinger's Quantum Theory, Physical Review,
vol 28,pp. 695–710 (1926)

• Heydenburg, N.P., Phys. Rev. 46, 1069 (1934)

• Zettili, N., Quantum Mechanics: Concepts and Applications, Chichester, U.K: Wiley, (2009)

• http://hyperphysics.phy-astr.gsu.edu/hbase/Atomic/stark.html

• https://quantummechanics.ucsd.edu/ph130a/130_notes/node337.html
Thank You…

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