PHY5052(Cold Atom Physics)

Chapter 1: Atomic structure

2023.02.24
 Recall on last class
Uncertainty principle:
1 𝑥, 𝑝Ƹ = 𝑖ℏ, so
ΔA · ΔB ⩾ መ 𝐵෠
𝐴,
2 ℏ
Δ𝑥Δ𝑝 ⩾
Perturbation theory: 2
0 ȁ𝐻 ′ ȁ𝜓 0 ۧ
‫𝑚𝜓ۦ‬ 2 0 ȁ𝐻 ′ ȁ𝜓 0 ۧ
‫𝑚𝜓ۦ‬
𝑛 𝑛
𝐸𝑛 = 𝐸𝑛0 + ‫𝑛𝜓ۦ‬0 ȁ𝐻 ′ ȁ𝜓𝑛0 ۧ + ෍ 𝜓𝑛 = 𝜓𝑛0 + ෍ 0
𝜓𝑚
𝐸𝑛0 − 𝐸𝑚
0
𝐸𝑛0 − 𝐸𝑚
0
𝑚≠𝑛 𝑚≠𝑛
Angular momentum:
𝐿𝑖 , 𝐿𝑗 = 𝑖ℏ𝜖𝑖𝑗𝑘 𝐿𝑘 𝐿2 , 𝐿𝑖 = 0 𝑖, 𝑗 = 𝑥, 𝑦, 𝑧

Spherical tensor: 𝐿+ , 𝐿− = 2ℏ𝐿𝑧 𝐿𝑧 , 𝐿± = ±ℏ𝐿± 𝐿2 , 𝐿± = 0

Eigen values:
𝐿2 𝑓𝑙𝑚 = ℏ2 𝑙(𝑙 + 1)𝑓𝑙𝑚 𝐿𝑧 𝑓𝑙𝑚 = ℏ 𝑚𝑓𝑙𝑚
𝑚 = −𝑙, −𝑙 + 1, … , 𝑙 − 1, 𝑙
𝑙 must be an integer or a half-integer
General for all AMs
2
 Recall on last class
Addition of 2 AMs:

Total J still satisfies:

Just like an independent AM

𝑚 = 𝑚1 + 𝑚2 AM conservation

𝑗1 − 𝑗2 ≤ 𝑗 ≤ 𝑗1 + 𝑗2 Triangle rule

Wigner-Eckart theorem:
𝑗 𝑘 𝑗′
𝑛𝑗𝑚 𝑇෠𝑞𝑘 𝑛′ 𝑗 ′ 𝑚′ = −1 𝑗−𝑚 𝑛𝑗 ȁ𝑇෠ 𝑘 ȁ 𝑛′ 𝑗 ′
−𝑚 𝑞 𝑚′
3
 Eigenvectors of orbital AM
The orbital AM:
𝑳=𝒓×𝒑
Spherical coordinates:
ℏ 𝜕 1 𝜕 ℏ 𝜕
𝑳= [𝜙෠ − 𝜃መ ] 𝐿𝑧 =
𝑖 𝜕𝜃 𝑠𝑖𝑛 𝜃 𝜕𝜙 𝑖 𝜕𝜙

2
1 𝜕
2
𝜕 1 𝜕2
𝐿 = −ℏ [ 𝑠𝑖𝑛 𝜃 + 2 2
]
𝑠𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 𝑠𝑖𝑛 𝜃 𝜕𝜙

Eigen states:
𝐿2 𝑓𝑙𝑚 = ℏ2 𝑙(𝑙 + 1)𝑓𝑙𝑚 𝐿𝑧 𝑓𝑙𝑚 = 𝑚ℏ𝑓𝑙𝑚

44
 Eigenvectors of orbital AM
The orbital AM: 𝑳=𝒓×𝒑 2
1 𝜕 𝜕 1 𝜕
𝐿2 = −ℏ2 [ 𝑠𝑖𝑛 𝜃 + ]
Eigen states: 𝑠𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 𝑠𝑖𝑛2 𝜃 𝜕𝜙 2
𝐿2 𝑓𝑙𝑚 = ℏ2 𝑙(𝑙 + 1)𝑓𝑙𝑚 𝐿𝑧 𝑓𝑙𝑚 = 𝑚ℏ𝑓𝑙𝑚

𝐿𝑧 𝑓𝑙𝑚 = 𝑚ℏ𝑓𝑙𝑚 ⇒ 𝑓 = 𝑔(𝜃)𝑒 𝑖𝑚𝜙

𝑚 = 0, ±1, ±2, ⋯
Utilizing the “ladder” operators:
ℏ 𝜕 𝜕
𝐿± = 𝑒 ±𝑖𝜙 [±𝑖 − 𝑐𝑜𝑡𝜃 ]
𝑖 𝜕𝜃 𝜕𝜙
As:
𝐿+ 𝑓𝑙𝑙 = 0 ⇒ 𝑓𝑙𝑙 = 𝑐𝑙 𝑒 𝑖𝑙𝜙 𝑠𝑖𝑛𝑙 𝜃

𝐿− 𝑓𝑙𝑚 ∝ 𝑓𝑙𝑚−1

All the eigenfunctions of the orbital AM can be obtained, which

turn out to be spherical harmonics 𝒀𝒎 𝒍 (𝜽, 𝝓). 55
 Eigenvectors of orbital AM
The eigenfunctions of the orbital AM are the spherical harmonics
𝒀𝒎
𝒍 (𝜽, 𝝓).
𝐿2 𝑌𝑙𝑚 𝜃, 𝜙 = 𝑙(𝑙 + 1) ℏ2 𝑌𝑙𝑚 𝜃, 𝜙
𝑌𝑙𝑚 𝜃, 𝜙 = 𝛩 𝜃 𝛷(𝜙)
𝐿𝑧 𝑌𝑙𝑚 𝜃, 𝜙 = 𝑚ℏ 𝑌𝑙𝑚 𝜃, 𝜙

where: Θ(θ) = 𝐴𝑃𝑙𝑚 cosθ 𝑚

𝑚 𝑑
𝑖𝑚𝜙 𝑃𝑙𝑚 𝑥 = 1 −𝑥 2 2
𝑃𝑙 (𝑥)
Φ 𝜙 =𝑒 𝑑𝑥
𝑙
1 𝑑
𝑃𝑙 (𝑥) ≡ 𝑙 𝑥2 − 1 𝑙
2 𝑙! 𝑑𝑥

The spherical harmonics:

2𝑙 + 1 𝑙 − 𝑚 ! 𝑚
𝑌𝑙𝑚 𝜃, 𝜙 = −1 𝑚 𝑃𝑙 cosθ 𝑒 ⅈ𝑚𝜙
4𝜋 𝑙+𝑚 !

The quantum number l is called the orbital quantum number

and m the magnetic quantum number
6
 Eigenvectors of orbital AM
Several lowest spherical harmonics:

Easily plotted in Mathematica, matlab, Python

7
 Eigenvectors of orbital AM
Traditionally, atomic states (l, m) are labeled with Latin letters

𝑙 statelabel 𝑚 statelabel
0 𝑠 0 𝜎
1 𝑝 1 𝜋
2 𝑑 2 𝛿
3 𝑓 3 𝜑
4 𝑔 4 𝛾

8
Corresponding chapters in C. Foot: 2, 3, 4, 5, 6

But re-organized:

1. Electronic structure: H (1 e-), He (2 e-) and

alkaline atoms (H-like)
2. Fine structure: relativistic effect
3. Hyperfine structure: nuclear spin
4. Atom in external field: Zeeman and Stark effects

11
 Why H atom again?

Science 365, 1007–1012 (2019)

By measuring the Lamb shift
13
 The Schrodinger equation for H or H-like ions
The Schrodinger equation of electron only:
-
𝜕𝜓 ℏ2 2
𝑖ℏ =− 𝛻 𝜓 + 𝑉𝜓
𝜕𝑡 2𝑚
For H or H-like ions:
+
𝑍𝑒 2 1
𝑉 𝑟 =−
4𝜋𝜖0 𝑟
The stationary Schrodinger equation of electron:

ℏ2 𝛻 2 𝑍𝑒 2
− − 𝜓 = 𝐸𝜓
2𝑚 4𝜋𝜖0 𝑟

14
 The Schrodinger equation for H or H-like ions
Take the nuclear motion into account
ℏ2 2 ℏ2
𝐾. 𝐸. =− 𝛻𝑒 − 𝛻𝑁 2
2𝑚 2𝑀
Write things in terms of relative coordinates:
𝑀 𝒓𝑵 + 𝑚 𝒓𝒆
𝑹= 𝒓 = 𝒓𝒆 − 𝒓𝑵
𝑀+𝑚
ℏ2 𝛻𝑅2 ℏ2 𝛻𝑟2 𝑍𝑒 2
− − − 𝜓(𝑹, 𝒓) = 𝐸𝜓(𝑹, 𝒓)
2 𝑀+𝑚 2𝜇 4𝜋𝜖0 𝑟 𝑚𝑀
𝜇= ≈ 𝑚𝑒
𝑚+𝑀
Where M is the nuclear mass, 𝑚 = 𝑚𝑒 is much smaller than M.
𝜇 is the reduced mass
Separate the COM motion and the relative motion: 𝜓 𝑹, 𝒓 = 𝑓 𝒓 𝑔 𝑹 , get
ℏ2 𝛻𝑅2
− 𝑔 𝑹 = 𝐸𝑔 𝑔 𝑹 (C.O.M motion)
2 𝑀+𝑚

ℏ2 𝛻𝑟2 𝑍𝑒 2
− − 𝑓 𝒓 = 𝐸𝑓 𝑓 𝒓 (rel. motion)
2𝜇 4𝜋𝜖0 𝑟
15
 The Schrodinger equation for H or H-like ions
COM motion: external degrees of freedom, translational, temperature
(control with cooling and trapping, topics for later chapters)

ℏ2 𝛻𝑅2
− 𝑔 𝑹 = 𝐸𝑔 𝑔 𝑹
2 𝑀+𝑚

The relative motion gives the internal structures (topics of this chapter),
rename 𝑓 𝒓 → 𝜓 𝒓 , 𝐸𝑓 → 𝐸, 𝜇 → 𝑚 , we have

ℏ2 𝛻𝑟2 𝑍𝑒 2
− − 𝜓 𝒓 = 𝐸𝜓 𝒓
2𝑚 4𝜋𝜖0 𝑟

This chapter focus on the relative motion

16
 The Schrodinger equation for H or H-like ions
Spherical coordinate:
ℏ2 1 𝜕 2
𝜕 1 1 𝜕 𝜕 1 1 𝜕 2
− 𝑟 + 2 sinθ + 2 2 𝜓 + 𝑉𝜓 = 𝐸𝜓
2𝑚 𝑟 2 𝜕𝑟 𝜕𝑟 𝑟 sinθ 𝜕𝜃 𝜕𝜃 𝑟 sin 𝜃 𝜕𝜑 2

Central potential: 𝑉 = 𝑉(𝑟)

𝜓 = 𝑅 𝑟 𝑌 𝜃, 𝜑
2
1 𝑑 𝑑𝑅 2𝑚𝑟
𝑟2 − 2 (𝑉(r) − 𝐸)
𝑅 𝑑𝑟 𝑑𝑟 ℏ
1 1 𝜕 𝜕𝑌 1 𝜕2𝑌
+ 𝑠𝑖𝑛𝜃 + 2 2
=0
𝑌 𝑌𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑌𝑠𝑖𝑛 𝜃 𝜕𝜑

Can separate into:

1 𝑑 𝑑𝑅 2𝑚𝑟 2
Radial part: 𝑟2 − 2 𝑉 𝑟 −𝐸 =𝜆
𝑅 𝑑𝑟 𝑑𝑟 ℏ
1 𝜕 𝜕𝑌 1 𝜕2𝑌
Angular part: 𝑠𝑖𝑛𝜃 + = −𝜆
𝑌𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑌𝑠𝑖𝑛2 𝜃 𝜕𝜑2
17
 The Schrodinger equation for H or H-like ions
The angular part:
1 𝜕 𝜕𝑌 1 𝜕2𝑌
𝑠𝑖𝑛𝜃 + = −𝜆
𝑌𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑌𝑠𝑖𝑛2 𝜃 𝜕𝜑2
Remember:
1 𝜕 𝜕 1 𝜕 2
𝐿2 = −[ 𝑠𝑖𝑛 𝜃 + ]
𝑠𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 𝑠𝑖𝑛2 𝜃 𝜕𝜙 2

The angular part is exactly the orbital AM, i.e. spherical harmonics 𝒀𝒎
𝒍 (𝜽, 𝝓)
are the eigenfunctions of the angular part
𝑌𝑙𝑚 𝜃, 𝜙 = 𝛩 𝜃 𝛷(𝜙)
2𝑙 + 1 𝑙 − 𝑚 ! 𝑚
𝑌𝑙𝑚 𝜃, 𝜙 = −1 𝑚
𝑃𝑙 cosθ 𝑒 ⅈ𝑚𝜙
4𝜋 𝑙 + 𝑚 !
is the eigen function of the angular part:
𝐿2 𝑌𝑙𝑚 𝜃, 𝜙 = 𝑙(𝑙 + 1) ℏ2 𝑌𝑙𝑚 𝜃, 𝜙
𝐿𝑧 𝑌𝑙𝑚 𝜃, 𝜙 = 𝑚ℏ 𝑌𝑙𝑚 𝜃, 𝜙
The quantum number l is called the orbital quantum number
and m the magnetic quantum number 18
 Solution of the angular equation
Traditionally, atomic states (l, m) are labeled with Latin letters

𝑙 statelabel 𝑚 statelabel
0 𝑠 0 𝜎
1 𝑝 1 𝜋
2 𝑑 2 𝛿
3 𝑓 3 𝜑
4 𝑔 4 𝛾

23
 Solution of the radial equation
The radial equation:
𝜆 = 𝑙(𝑙 + 1)
1 𝑑 2
𝑑𝑅 2𝑚𝑟 2
𝑟 − 2 𝑉 𝑟 −𝐸 =𝜆
𝑅 𝑑𝑟 𝑑𝑟 ℏ 𝑒2 1
𝑉 𝑟 =−
Define: 4𝜋𝜖0 𝑟
𝑢(𝑟) ≡ 𝑟𝑅(𝑟)

Get:
ℏ2 𝑑 2 𝑙 𝑙 + 1 ℏ2
− + + 𝑉(𝑟) 𝑢 𝑟 = 𝐸𝑢 𝑟
2𝑚 𝑑𝑟 2 2𝑚𝑟 2

𝑙 𝑙 + 1 ℏ2
𝑉eff 𝑟 =𝑉 𝑟 + effective potential
2𝑚𝑟 2

centrifugal term

Solving the radial equation is just a problem of finding the energy levels in the
effective potentials
24
 Solution of the radial equation
𝑒 2 1 𝑙 𝑙 + 1 ℏ2
𝑉eff 𝑟 =− + an effective potential with AM centrifugal barrier
4𝜋𝜖0 𝑟 2𝑚𝑟 2
For 𝑙 ≠ 0, the centrifugal barrier prevents the wavefunction from
reaching the origin

Blue: l = 0
Yellow: l = 1 to 5

25
 Solution of the radial equation
To solve:
ℏ2 𝑑 2 𝑙 𝑙 + 1 ℏ2 𝑒2
− + − 𝑢 𝑟 = 𝐸𝑢 𝑟
2𝑚 𝑑𝑟 2 2𝑚𝑟 2 4πϵ0 𝑟 −2𝑚 𝐸
𝜅≡
ℏ
𝑚𝑒 2
Get: 𝜌 ≡ 𝜅𝑟 , and 𝜌0 ≡ 2
2πϵ0 ℏ 𝜅
𝑑2𝑢 𝜌0 𝑙 𝑙 + 1
= 1− + 𝑢
𝑑𝜌2 𝜌 𝜌2

Asymptotic behavior:
ⅆ2𝑢
𝜌 → ∞, = 𝑢, 𝑢 𝜌 = 𝐴𝑒 −𝜌 + 𝐵𝑒 𝜌 , 𝐵=0
ⅆ𝜌2
ⅆ2𝑢 𝑙 𝑙+1
𝜌 → 0, = 𝑢, 𝑢 𝜌 = 𝐶𝜌𝑙+1 + 𝐷𝜌−𝑙 , 𝐷=0
ⅆ𝜌2 𝜌2

Generally:
𝑢 𝜌 = 𝜌𝑙+1 𝑒 −𝜌 𝑣(𝜌)
ⅆ2𝑣 ⅆ𝑣
𝜌 2 +2 𝑙+1−𝜌 + 𝜌0 − 2 𝑙 + 1 𝑣 =0
ⅆ𝜌 ⅆ𝜌

For detailed solution, see Ch4.3 in Griffiths “Introduction to QM” 26

 Solution of the radial equation
To solve: ⅆ2𝑣 ⅆ𝑣
𝜌 2 +2 𝑙+1−𝜌 + 𝜌0 − 2 𝑙 + 1 𝑣 =0
ⅆ𝜌 ⅆ𝜌

Assume a power series solution:

∞

𝑣 𝜌 = ෍ 𝑎𝑗 𝜌 𝑗
Get: 𝑗=0
∞ ∞ ∞ ∞

෍ 𝑗(𝑗 + 1)𝑎𝑗+1 𝜌 𝑗 + 2 𝑙 + 1 ෍ 𝑗 + 1 𝑎𝑗+1 𝜌 𝑗 − 2 ෍ 𝑗𝑎𝑗 𝜌 𝑗 + 𝜌0 − 2 𝑙 + 1 ෍ 𝑎𝑗+1 𝜌 𝑗 = 0

𝑗=0 𝑗=0 𝑗=0 𝑗=0

2 𝑗 + 𝑙 + 1 − 𝜌0
Therefore: 𝑎𝑗+1 = 𝑎
(𝑗 + 1)(𝑗 + 2𝑙 + 2) 𝑗

For large 𝑗, 2 2𝑗
𝑎𝑗+1 ~ 𝑎 𝑎𝑗 ≅ 𝐴 with 𝑎0 = 𝐴
i.e. large 𝜌: 𝑗+1 𝑗 𝑗!
∞
Finally: 2𝑗 𝑗
𝑣 𝜌 = 𝐴 ෍ 𝜌 = 𝐴𝑒 2𝜌 𝑢 𝜌 = 𝐴𝜌𝑙+1 𝑒 𝜌
𝑗!
𝑗=0

Again 𝒖 → ∞, when 𝝆 → ∞ 𝒂𝒋𝒎𝒂𝒙+𝟏 = 𝟎 27

 Solution of the radial equation
As: 2 𝑗 + 𝑙 + 1 − 𝜌0
𝒂𝒋𝒎𝒂𝒙+𝟏 = 𝟎 𝑎𝑗+1 = 𝑎
(𝑗 + 1)(𝑗 + 2𝑙 + 2) 𝑗

Then:
2(𝑗𝑚𝑎𝑥 + 𝑙 + 1) − 𝜌0 = 0

Defining: 𝑛 ≡ 𝑗𝑚𝑎𝑥 + 𝑙 + 1 𝜌0 = 2𝑛
−2𝑚 𝐸 𝑚𝑒 2
𝜅≡ 𝜌0 ≡
ℏ 2πϵ0 ℏ2 𝜅
Finally:
ℏ2 𝜅 2 𝑚𝑒 4
𝐸=− =− 2 2 2 2
2𝑚 8π ϵ0 ℏ 𝜌0
2
𝑚 𝑒2 1
𝐸𝑛 = − 2 𝑛 = 1, 2, 3, …
ℏ 4πϵ0 2𝑛2

Interestingly the energy is independent on the orbital angular momentum l

𝑙 ≤𝑛−1
28
Solution of the radial equation

29
 Solution of the radial equation
2
𝑚 𝑒2 1
𝐸𝑛 = − 2 𝑛 = 1, 2, 3, …
ℏ 4πϵ0 2𝑛2
In atomic units,
1 1
𝐸𝑛 = − hartrees = −𝑅𝑦 2
2𝑛2 𝑛
2
𝑒2
1 hartree=𝑚𝑒
4πϵ0 ℏ

=27.2 ev =219474.6 cm-1= 6579.68392 THz =3.157746 × 105 Kelvin

The Rydberg constant:

𝑚𝑒 𝑒 2 2 𝑅𝑦 𝑚𝑒 𝑒 4
𝑅𝑦 = ( ) = 13.6 eV 𝑅∞ ≡ =
2 4𝜋𝜖0 ℏ ℎ𝑐 8𝜖0 2 ℎ3 𝑐
= 10973731.568160(21) m−1

30
 Solution of the radial equation
The famous Bohr radius
4π ϵ0ℏ2
𝑎0 ≡ = 5.29 10-11 m=0.529 Å
𝑚𝑒 𝑒2
1
Then: 𝐸𝑛 = − hartrees
2𝑛2
ℏ2 1 𝑒2 1
𝐸𝑛 = − =−
𝑚𝑎0 2 2𝑛2 4π ϵ0𝑎0 2𝑛2

1 hartree is just the Coulumb energy between electron and

proton for 1s electron of H

Note : the energy levels of H are highly degenerate. For a given n,

1) l has n values: 𝒍 ≤ 𝒏 − 𝟏
2) m has 2l+1 values with each l
3) total degeneracy: n2

31
 Solution of the radial equation
Other nature units defined from H atom in ground state

𝛼: Fine structure constant

𝑒2 1
𝛼= ≅
4𝜋𝜖0 𝑐ℏ 137

𝐸𝑛𝑒𝑟𝑔𝑦: 𝛼 2 𝑚𝑐 2

𝑉𝑒𝑙𝑜𝑐𝑖𝑡𝑦: 𝛼 𝑐 = 𝑐/137

𝑒
𝐸 − 𝑓𝑖𝑒𝑙𝑑:
4𝜋𝜖0 𝑎02

32
Solution of the radial equation

Wavelength of the Balmer series

Wavelength
Transition Color
(nm)
383.5384 9→2 Violet
388.9049 8→2 Violet
397.0072 7→2 Violet
410.174 6→2 Violet
434.047 5→2 Violet
Bluegreen
486.133 4→2
(cyan)
656.272 3→2 Red
656.2852 3→2 Red

33
 Solution of the radial equation
The wave function:
2 3 𝑛 − 𝑙 − 1 ! −𝑟/𝑛𝑎 2𝑟 𝑙 2𝑙+1 2𝑟 𝑚
𝜓𝑛𝑙𝑚 = ( ) 3
𝑒 ( ) 𝐿 𝑛−𝑙−1 𝑟 𝑌𝑙 (𝜃, 𝜙)
4𝑛𝑎 2𝑛[ 𝑛 + 𝑙 !] 𝑛𝑎 𝑛𝑎

𝜓𝑛𝑙𝑚 𝑟, 𝜃, 𝜙 = 𝑅𝑛𝑙 𝑟 𝑌𝑙𝑚 (𝜃, 𝜙)

For detailed solution, see Ch4.3 in Griffiths “Introduction to QM” 35

 Solution of the radial equation: wave function
Illustration for the radial wavefunction (from Wolfram.com demo).
Each u(r) has (n - l - 1) nodes (except for r=0) and for l ≠ 0, the
wavefunction vanishes at the origin.

𝑢2 𝑢2

l=0 l≠0

36
 Solution of the radial equation: some scaling rules
1. At short range, for fixed l, the wave function is independent of n except for a
scaling n3/2 due to normalization. This gives rise to many 1/n3 scaling laws.
2. For fixed n, changing l affects only the short - range wave function (centrifugal
correction vanishes at long range, compared to Coulomb interaction).
3. size scales as n2
1
𝑟 = 𝑅𝑛𝑙 ❘𝑟❘𝑅𝑛𝑙 = 3𝑛2 − 𝑙 𝑙 + 1 𝑎0 ∝ 𝑛2
2
4. Energy spacing scales as 1/n3
1 1 2𝑅𝑦
ΔE =𝑅𝑦 − ≃ 3
𝑛2 𝑛+1 2 𝑛
5. Some other expectation values:
1 1 1
= 2 ∝ 2
𝑟 𝑛 𝑎0 𝑛 1 1 1 1
= ∝
𝑟3 𝑎0 3 𝑛3 (𝑙 + 1)(𝑙 + 1/2)𝑙 𝑛3
1 1 1 1
= ∝
𝑟2 𝑎0 2 𝑛3 𝑙 + 1Τ2 𝑛3
37
 Application to Rydberg atoms
Rydberg atoms: highly excited atoms with one electron far away
large n 𝑟 ∝ 𝑛2
The schematic structure and the effective potential

Similar situation for all atoms, not only hydrogen!

38
 Application to Rydberg atoms
The large n spectrum is almost like hydrogen : one charge
Ry
𝐸𝑛𝑙 =− 2
𝑛
In reality, need to consider the quantum defect (electron penetrating
into the “core”): 𝛿𝑛𝑙

Ry
𝐸𝑛𝑙 =−
(𝑛 − 𝛿𝑛𝑙 )2

Similar properties (scaling rules) as hydrogen atoms with large n: have a

large electric dipole moment, although the atom is still neutral.

𝑟 ∝ 𝑛2
𝑑 = 𝑒𝑟Ԧ ∝ 𝑛2

39
 Application to Rydberg atoms
Other scaling laws for Rydberg atoms
properties scaling
Energy 1/n2
Energy spacing 1/n3
Radius and electric dipole moment n2
Radiative lifetime n3
Polarizability n7
Dipole-dipole interaction of 2 Rydberg n4
atoms
Van-del Waals interaction (𝐶6 ) n11
𝑟 𝑠 ∝ 𝑛2𝑠
𝑟 −𝑠 ∝ 𝑛−3 for 𝑠 > 1
Rydberg atom is an important subfield in AMO physics. For more:
Gallagher, Thomas F. (1994). Rydberg Atoms. Cambridge
University Press. ISBN 0-521-02166-9.
And a lot of review articles 40
 Application to Rydberg atoms
Rydberg atoms can have strong interactions
Dipole-dipole interaction n4
Van-del Waals interaction (𝐶6 ) n11

Rydberg blockade:
direct as quantum gate
operation

And many other

applications: a very
hot topic

41
 Non-relativistic hydrogen: summary
The total wave function: 𝜓𝑛𝑙𝑚 𝑟, 𝜃, 𝜙 = 𝑅𝑛𝑙 𝑟 𝑌𝑙𝑚 (𝜃, 𝜙)

2 3 𝑛 − 𝑙 − 1 ! −𝑟/𝑛𝑎 2𝑟 𝑙 2𝑙+1 2𝑟 𝑚
𝜓𝑛𝑙𝑚 = ( ) 3
𝑒 ( ) 𝐿 𝑛−𝑙−1 𝑟 𝑌𝑙 (𝜃, 𝜙)
4𝑛𝑎 2𝑛[ 𝑛 + 𝑙 !] 𝑛𝑎 𝑛𝑎
View 3-D H atom wavefunction at :
http : // www.falstad.com/qmatom/

Traditionally, atomic states (l, m) are labeled with Latin letters

𝑙 statelabel 𝑚 statelabel
0 𝑠 0 𝜎
1 𝑝 1 𝜋
2 𝑑 2 𝛿
3 𝑓 3 𝜑
4 𝑔 4 𝛾

42
 Non-relativistic hydrogen: summary
The energy:
1 𝑒2 1 𝑅𝑦
𝐸=− =− 2
2 4πϵ0 𝑎0 𝑛2 𝑛
with: 𝑚𝑒 𝑒 4
4πϵ0 ℏ2
𝑎0 = 𝑅𝑦 = 2 2
𝑚𝑒 2 2ℏ 4𝜋𝜖0
𝑟 ∝ 𝑛2
For non − relativist H, 𝑙 and m are degenerate.
For H − like alkali atoms, the 𝑙 degeneracy is removed.

Also for hydrogen like atoms

𝐻𝑒 + , 𝐿𝑖 2+ ,
𝑅𝑦𝑑𝑏𝑒𝑟𝑔 atoms (need quantum defect for the core),
alkali atoms (also need quantum defect)

43
 Non-relativistic hydrogen: summary
The total wave function:
𝜓𝑛𝑙𝑚 𝑟, 𝜃, 𝜙 = 𝑅𝑛𝑙 𝑟 𝑌𝑙𝑚 (𝜃, 𝜙)

2 3 𝑛 − 𝑙 − 1 ! −𝑟/𝑛𝑎 2𝑟 𝑙 2𝑙+1 2𝑟 𝑚
𝜓𝑛𝑙𝑚 = ( ) 𝑒 ( ) 𝐿 𝑛−𝑙−1 𝑟 𝑌𝑙 (𝜃, 𝜙)
4𝑛𝑎 2𝑛[ 𝑛 + 𝑙 !]3 𝑛𝑎 𝑛𝑎

Including the electronic spin:

Spin angular momentum operator: s
𝑠 2 𝜒 = 𝑠(𝑠 + 1)𝜒; 𝑠𝑧 𝜒 = 𝑚𝑠 𝜒
with s = 1/2, and ms = ±1/2
1
𝜒 are the spin eigenfunction: 𝑠𝑧 𝜒 ± = ± 𝜒 ±
2
So now we have 4 quantum numbers to describe the electron
in an atom 𝑛, 𝑙, 𝑚𝑙 , 𝑚𝑠

The total wavefunction is

𝝍𝒏,𝒍,𝒎𝒍,𝒎𝒔 =R𝒏𝒍 (𝒓)𝒀𝒎
𝒍 (𝜽, 𝝋)𝝌
𝒎𝒔

44
 Non-relativistic hydrogen: summary
Parity: important for selection rules
In spherical coordinates, parity operation 𝑃෠ (ො𝒓 → −ො𝒓) is equivalent
to let:
𝑟→𝑟
𝜃 → 𝜋 − 𝜃: a reflection
𝜙 → ϕ + 𝜋: a rotation

For the total wavefunction ψnlm (r, θ, φ), parity is odd or even only
depending on the value of l

෠ 𝑛𝑙𝑚 𝑟, 𝜃, 𝜑 = −1 𝑙 𝜓𝑛𝑙𝑚 𝑟, 𝜃, 𝜑
𝑃𝜓

45