Zeeman Effect

• Hydrogen Atom: 3D Spherical Coordinates

– Ψ = (spherical harmonics)(radial) and probability density P
– E, L2, Lz operators and resulting eigenvalues

• Angular momenta: Orbital L and Spin S

– Addition of angular momenta
– Magnetic moments and Zeeman effect
– Spin-orbit coupling and Stern-Gerlach (Proof of electron
spin s)

• Periodic table
– Relationship to quantum numbers n, l, m
– Trends in radii and ionization energies
 Schrödinger Equation: Coordinate Systems
Potential
1D Cartesian Kinetic energy Total energy
ℏ 2 d 2ψ ( x )
energy
− 2
+ V ( x )ψ ( x ) = Eψ ( x )
2m dx

3D Cartesian Kinetic energy Potential energy Total energy

ℏ2  ∂2 ∂2 ∂2 
−  2 + 2 + 2 ψ (x ) + V (x, y, z )ψ (x ) = Eψ (x )
2m  ∂x ∂y ∂z 

Convert to spherical using: x = r sin θ cos φ , y = r sin θ sin φ , z = r cosθ

3D Spherical Kinetic energy Potential

energy
ℏ 2 1 ∂  2 ∂ψ  ℏ2  1 ∂  ∂ψ  1 ∂ 2ψ 
−  r  −   sin θ + 2 2 
+V ( r )ψ
2 µ r ∂r  ∂r  2 µ r 2
2
 sin θ ∂θ  ∂θ  sin θ ∂φ 
= Eψ
Total energy
 Hydrogen Atom: 3D Spherical Schrödinger Equation
“Rewritten” Schrodinger Eqn.:
pˆ 2 1 ∂  2 ∂ 
ψ (r ,θ , Q ) + Veff ψ (r ,θ , Q ) = Enψ (r ,θ , Q ) where pˆ 2 = − ℏ 2 r
r ∂ r  ∂ r 
2 
2µ

Eigenfunctions:
ψ nlm (r , θ , φ ) = R n (r ) Y lm (θ , φ )
Laguerre Spherical
Polynomials Harmonics

2
− z E0 2
1  ke 2

Eigenvalues: En = where E0 =   µ ≈ 13.6eV

n2 2 ℏ 
 Hydrogen Atom: 3D Spherical Schrödinger Equation

3 Quantum Numbers (3-dimensions)

n = energy level value (average radius of orbit)

n = 1, 2, 3 …

l = angular momentum value (shape of orbit)

l = 0, 1, 2, … (n – 1)

m = z component of l (orientation of orbit)

m = -l,(-l + 1) ..0,1,2,..+l

How many quantum states (n, l, m) exist for n = 3? Is there a general

formula?
 Wave Functions : Formulas

n=1

l=0

n=2

l=1
 Wave Functions: Angular Component

m = –2 m = –1 m=0 m=1 m=2

l=0 s-orbital

l=1 p-orbitals

sinθ sinφ cosθ sinθ cosφ

l = 2 d-orbitals

sin2θ sin2φ sinθcosθ 3cos2θ–1 sinθcosθ sin2θ cos2φ

sinφ cosφ
 Wave Function: Radial
Component

http://cwx.prenhall.com/bookbind/pubbooks/giancoli3/chapter40/multiple3/deluxe-content.html

What is the relationship between the number of zero crossings for the radial
component of the wave function and the quantum numbers n and l?
 Wave Functions: Angular & Radial Components
l = 0 s-orbitals
From: http://pcgate.thch.uni-bonn.de/tc/people/
hanrath.michael/hanrath/HAtomGifs.html
l=1 p-orbitals
100

l=2 d-orbitals
200 211 210 211

300 311 310 311 322 321 320 321 322

400 411 410 411 422 421 420 421 422

l=3 f-orbitals

433 432 431 430 431 432 433

 Probability Density: Formula

P = ∫ψ ∗ψ (r ,θ ,φ )dV
∞ π 2π
= ∫ ∫ ∫ ψ ∗ψ r 2 sin θ dϕ dθ dr
0 0 0

Volume Element dV

∞
P = 4π ∫ψ ∗ψ r 2 dr for spherically symmetricψ
0
∞
P = ∫ P (r ) dr where P ( r ) = ( 4π r 2 )ψ ∗ψ
0

⇒For small ∆r, can use P = P(r) ∆ r (analogous to 1D case)

 Probability Density: “Density” Plots
2 2 2
ψ 200 n=2 ψ 210 n=2 ψ 21 ± 1
s-orbital p-orbitals
l=0 l=1

m=0

m=1

“Spherical Shells” “Dumbbells”

 Probability Density: Cross Sections

http://webphysics.davidson.edu/faculty/dmb/hydrogen/default.html

Can you draw the radial probability functions for the 2s to 3d wave functions?
 Probability Density: Cross Sections

http://cwx.prenhall.com/bookbind/pubbooks/giancoli3/chapter40/multiple3/deluxe-content.html

Rank the states (1s to 3d) from smallest to largest for the electron’s most
PROBABLE radial position.
For which state(s) do(es) the most probable value(s) of the electron's position
agree with the Bohr model?
 Probability Density: Problem

For the ground state n = 1, l = 0, m = 0 of hydrogen, calculate the

probability P(r)∆r of finding the electron in the range ∆r = 0.05ao at r = ao/2

P100 (r )∆r = (4π r 2 ) [ Ψ100 (r )] ∆r

2

e− r ao
e−2r ao
where Ψ100 (r ) = and [ Ψ100 (r )]2
=
π a1.5
o π ao3

 − ao ao 
e
P100 (ao )∆r = (π ao2 ) 
 π a3 
(0.05ao )
 o 
after substitution of r , Ψ100 , and ∆r

P100 (ao )∆r = e−1 (0.05) = 0.018

 Orbital Angular Momentum L:
Related to Orbital “Shape”

• Magnitude of Orbital Angular Momentum L

 1 ∂  ∂  1 ∂ 
Lˆ2ψ ( r ,θ ,φ ) = −ℏ 2   sin θ  + 2 
ψ = l ( l + 1) ℏ 2
ψ
 sin θ ∂θ  ∂θ  sin θ ∂φ 
2

Eigenvalues: L = l ( l + 1) ℏ

• Z-component of L
∂
Lzψ ( r ,θ ,φ ) = −iℏ ψ = mℏψ
ˆ
∂φ
Eigenvalues: Lz = mℏ
 Orbital Momentum L: Vector Diagram
For l = 2, find the magnitude of the angular momentum L and the possible m
values. Draw a vector diagram showing the orientations of L with the z axis.

l=2 z L = √6h = 2.45h

L = l (l +1) ℏ = 2(2+1) ℏ 2h m=2

55º
L = 6 ℏ or 2.45 ℏ h m=1
24º
m=0
m = −l to l = 0, ± 1 ± 2 −h m = −1
Lz = m ℏ = 0, ± 1ℏ, ± 2ℏ −2h m = −2

Can you draw the vector diagram for l = 3? For j = 3/2?

 Spin Angular Momentum S:
Property of Electron

• Magnitude of Spin Angular Momentum S

Eigenvalues: S = s ( s + 1) ℏ
11  3
For one electron: S =  + 1 ℏ = ℏ
22  4

Example for s = 1/2

• Z-component of S z s = √0.75h
Eigenvalues: S z = ms ℏ
h/2 m = 1/2
ℏ
For one electron: Sz =
2
-h/2 m = −1/2
 Angular Momentum: Link to Magnetic Moments
• Orbital angular momentum L and spin angular momentum s of
electrons result in magnetic moments µl and µs.

   qv  2 q qL
Remember that µ = i A →   π r = ( vr ) =   where L = mvr
 2π r  2 2m

Orbital l = 0, 1, 2, … Spin: s = ½

 −gL µB   − gs µB 
µl = L = l ( l + 1) g L µ B µs = s = s ( s + 1) g s µ B
ℏ ℏ
z-component µlz = − ml g L µ B z-component µ sz = −ms g s µ B ≈ ± µ B


where µ B =
eℏ
= 5.79 × 10 −5 eV
and g L , g s = gyromagnetic ratios
2me T
 Zeeman Effect: Splits m values

• Orbital magnetic moment µL interacts with an external

magnetic field B and separates degenerate energy levels.
m=1
l=1 m=0
m = –1
NO B
B Field
Field

l=0 m=0

 
U = − µ ⋅ Bext ⇒ U = − µlz B Different energies for
different ml values!
assume z
direction
 “Anomalous” Zeeman Effect: More Lines??

Zeeman ????

ml = 1
l = 1 ml = 0
ml = –1
Add external
magnetic field

l = 0 ml = 0

Why are there more energy levels than expected from the Zeeman effect?
• Electron’s spin magnetic moment µs interacts with internal B field caused by its
orbital magnetic moment µl and separates energy levels.

Spin-Orbit Coupling: Splits j values

Spin up: j = 3/2

High Energy S L, Bl
l=1
e-
  s = 1/2
U = µ s ⋅ Bint = − µ sz B = ± µ B B ∆U = 2µ B B
v j = 1/2
µs p+

Spin down: µs
L, Bl
Low Energy
e- l=0
v j = 1/2
S p+ s = 1/2
 Angular Momentum Addition: L + S gives J
 
• Special Case: L+S
Vectors Quantum Numbers
  
J = L+S j = l + s, l − s

J = j ( j + 1)ℏ m j = − j , − j + 1,... j − 1, j

Example: l = 1, s = ½

j = 1 + 12 = 3
2
and j = 1 − 12 = 1
2

m j = − 32 ,− 12 , 12 , 32 and m j = − 12 , 12

j = 3/2 j = 1/2
 “Anomalous” Zeeman Effect: Spin-Orbit + Zeeman
Spin-Orbit Zeeman
mj = 3/2
mj = 1/2
mj = –1/2
j = 3/2 mj = –3/2
l = 1 s = 1/2
mj = 1/2
mj = –1/2
j = 1/2

mj = 1/2
l = 0 s = 1/2
j = 1/2 mj = –1/2

• Quantum numbers mj (j-j coupling) for HIGHER Z elements.

 Angular Momentum Addition: General Rules
 
• General Case: J1 + J 2
Vectors Quantum Numbers
  
J tot = J1 + J 2 j = ( j1 + j2 ), ( j1 + j2 − 1),... j1 − j2

J tot = j ( j + 1)ℏ m j = − j ,− j + 1,... j − 1, j

Example: j1 = 3/2, j2 = 3/2

jmax = 32 + 32 = 3 and jmin = 3

2
− 32 = 0
j = 3, 2, 1, 0
m j = −3, − 2, − 1, 0,1, 2, 3 for j = 3
 Stern-Gerlach Experiment: ALSO splits m values

 dB 
 Fz = µ z 
• A magnetic force  dz  deflects atoms up or down by an
amount that depends on its magnet moment and the B field gradient.

• For hydrogen (mlz = 0), two lines are observed (spin up, spin down).
– Since l = 0, this experiment gave direct evidence for the
existence of spin.

Case of ml = -1, 0, 1

What is the “story” of this experiment? Did Stern & Gerlach know about
 Stern-Gerlach Experiment: Problem
The angular momentum of the yttrium atom in the ground state is
characterized by the quantum number j = 5/2. How many lines would
you expect to see if you could do a Stern-Gerlach experiment with
yttrium atoms?
Remember that in the Stern-Gerlach experiment all of the atoms with
different mj values are separated when passing through an
inhomogeneous magnetic field, resulting in the presence of distinct
lines.

How many lines would you expect to see if the beam consisted of
atoms with l = 1 and s = 1/2?
 ke 2
Multi-electron Atoms Vint =  
r2 − r1

• Schrödinger equation cannot be solved exactly for multi-electron

atoms because Coulombic repulsion “mixes” variables.
– Estimate energies using single-electron wave functions and
“correcting” energies with 1st-order perturbation theory.

• Orbitals “fill” in table as follows: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p . .
– Only ONE electron per state (n, l, ml , ms ) - Pauli Exclusion Rule!
– Why is 4s filled before 3d? ⇒ 4s orbital has a small bump near
origin and “penetrates” shielding of core electrons better than 3d
orbital, resulting in a larger effective nuclear charge and lower
energy.
 Noble Gas
Group VI
Group IV
Group III
Alkali

Halogen
Group V
l = 0 (s) Periodic Table
n
l = 1 (p)
1
2 l = 2 (d)
3
4
5

6
7
l = 3 (f)
 Periodic Table: Trends for Radii and Ionization Energies
Maxima = alkali metals
• Effective atomic radii decrease
across each row of table.
– Why? Effective nuclear charge
increases and more strongly
attracts outer electrons,
decreasing their radius.

• Ionization energies increase Maxima = noble gases

across each row of table until the
complete “shell” is filled.
– Alkali atoms easily give up s-
orbital electrons.
– Halogens have strong affinity
for outer electrons.
 APPENDIX: Wave Functions Formulas
Spherical Component Yl,m Complete Wave Function ψn,l,m
s-orbital n=1 l=0
l=0
p-orbital n=2
m = ±1
l=1 l = 0,1

d-orbital
l=2

l = 1 m = ±1

f-orbital n=3
l=3
l = 0,1,2