Lecture 8

CHEM 209
Introductory Spectroscopy & Structure
Zeeman Splitting & MO Theory

Dr. W. S. Hopkins
30th September, 2015

Class Announcements
1. Assignment #1 due Friday

Notable Quote:
No amount of experimentation can ever prove me right; a single
experiment can prove me wrong.
--Albert Einstein

Lecture 7 Recap
Microstates & Zeeman Splitting
(A more) Complete picture of configurations, terms, levels,
& states
Multiple electron systems = rich spectrum
Hunds Rules help us determine energy ordering
External fields lift state degeneracy
(2J+1) state degeneracy for each level
(field free)
Magnetic Field = Zeeman Effect

3 | Slide

Lecture 8 Outlook
Zeeman Splitting & MO Theory
External fields lift state degeneracy
(2J+1) state degeneracy for each level (field free)
Magnetic Field = Zeeman Effect
2 Atomic Orbitals Combine To Make 2 Molecular Orbitals
Pieter Zeeman
Constructive Addition between nuclei = Bonding MO
Destructive Addition between nuclei = Anti-bonding MO 1865 - 1943
MO occupation Bond Order
MOs labelled based on symmetry
Linear molecule = axial symmetry
s, p, d,
u/g (only when centre of inversion)

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Top Hat Question

Lecture 8 Question 1
Atomic oxygen has a 1s2 2s2 2p4 configuration,
which gives rise to 3P, 1D, and 1S terms. What
is the term symbol for the ground electronic
state?

A. S0
1
B. D2
3
C. P2
1

D. P1
3
E. P0
3

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Top Hat Question

Lecture 8 Question 2
Under field free conditions, how many
degenerate quantum states are associated
with a 3P1 level?

A. 1
B. 2
C. 3

D. 4
E. 5

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Lifting State Degeneracy

L and S give rise to magnetic moments.
These can interact with an externally applied
magnetic field, B
(quantization
axis)

In the absence of external fields,

the 3 ML components of a 1P term
are degenerate
Interaction with an
external B field lifts this
degeneracy

Pieter Zeeman
1865 - 1943

This phenomenon is known as the Zeeman

Effect
Interaction Energy:

e
Where e
2me
magneton

E e M L B B M L B

and
B e

the Bohr
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The Normal Zeeman Effect

The Normal Zeeman Effect occurs for states where L
> 0 and S = 0

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The Anomalous Zeeman Effect

When S 0, the spin angular momentum also gives rise to a
magnetic moment
When both L and S are non-zero, splittings become
more complex:

E e g j J B e g j M J B

Where the Land gfactor,

g J ( LS ) 1

J J 1 S S 1 L( L 1)
2 J ( J 1)

gJ = 1.5 for a 3P2

gJ = 2.0 for a 3S1
level
level

Note when S = 0, J = L and gJ = 1, which

:
yields the expression for the
Normal Zeeman Effect

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The Anomalous Zeeman Effect

Energy levels are split into 2J+1 components dependent
on J, L, and S

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Example
A sodium atom is placed in a magnetic field with
B = 5.0 T. How is its ground electronic state
effected?

10 | Slide

Combining Atomic Orbitals (AOs)

Molecular orbitals (MOs) may be thought of
as combinations of atomic orbitals (AOs)
Hydrogen 1s
AO:

Radial
Wavefuncti
on

Constructive (in-phase)
addition:

Density Plot

Densit
y Plot

Schematic
Representati
on

Schematic
Representation

Spherical shape
maximum at
nucleus
decaying
exponentially
increased electron
density between
nuclei
(i.e. bond
formation)

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Anti-bonding Orbitals
Destructive (out-of-phase)
addition:

decreased electron
density between
nuclei
(i.e. anti-bonding)

Schematic
Representati
on

Rules for Atomic Orbital Combinations:

interaction inversely
proportional to
distance
interaction proportional to
2 AOs must combine along an axis of mutual
cosine of the alignment
. symmetry
angle
interaction inversely
3 AOs must be similar in size and
proportional to the
. energy
difference in size or energy
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1 AOs must be physically close enough to
. interact

Relative Energies of MOs

anti-bonding MO
(destabilization)
Out-of-phase
addition

AO basis set
In-phase
addition

bonding MO
(stabilization)

For MOs of similar symmetry the orbital with more nodes is

higher in energy
This method of generating MOs from AOs is
called Linear Combination of Atomic
Orbitals (LCAO)

Rule of Thumb: 2 AOs yield 2

MOs

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Non-spherical AOs (p-Orbitals)

4 unique
combinations
pz axial
alignment
1. in-phase
2. out-of-phase

u
O (2p)

g*
u

px & py off-axis
alignment
3. in-phase
4. out-of-phase

Px, Py
constructive
u
overlap

O (2p)

Pz
constructive
g
overlap

Pz
destructive
u
overlap

But what do the labels

Px, Py
destructive
g*
overlap
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MOs of Molecular Oxygen

u

-orbitals view along z-axis

u
O (2p)

g*

O (2p)

g*

uu

g
u

g
u

O (2s)

O (2s)

-orbitals view along z-axis

g
u
g

O
(1s)
u

g*

O (1s)

g
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MOs of Molecular Oxygen

u
g*
u
g
u
g

g vs. u inversion symmetry

Gerade, g, means even
unchanged when
inverting through
center of
symmetry

g*

Ungerade, u, means uneven

changes sign
when inverting
through center of
symmetry

u
g

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2nd Row Homonuclear Diatomics

u

Li2

Be2

B2

C2

N2

O2

F2

Ne2

g*

g
g*
u

u
g

Bond Order: 1

Bond Order = (# bonding electrons) (# anti-bonding electrons)

2
17 | Slide

Top Hat Question

Lecture 8 Question 3
What is the bond order of
+
Li
?
2
Li
u
g*
g

u
u
g

A. 0
B. 0.5
C. 1
D. 1.5
E. 2
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s-p mixing
Molecular orbitals can
interact too!
u
B (2p)

g*
g

B (2p)
pg

u
u
B (2s)

sg
B (2s)

B2

Mainly psome
(2s) g

Mainly ssome (2p) g

MOs should have the same

symmetry and be of similar
energies

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The Effect of Molecular Orbital

Mixing

u
2p

s-p mixing

g*
u

g*
2p

2p

2p

u
g
u
2s

u
2s

2s

2s

g
The degree to which s-p mixing takes
place depends on the energetic proximity
of the combining orbitals

Li2, Be2, B2, C2, N2

O2, F2, Ne2

s-p mixing significant

s-p mixing not significant

20 | Slide

The Effect of Molecular Orbital

Mixing

Li2, Be2, B2, C2, N2

O2, F2, Ne2

s-p mixing significant

s-p mixing not significant

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