Dr.

Usama El-Ayaan

:


Dr. Usama El-Ayaan

Dr. Usama El-Ayaan

Dr. Usama El-Ayaan


Gouy Balance

Dr. Usama El-Ayaan

Dr. Usama El-Ayaan

Dr. Usama El-Ayaan

mS+L = [4S(S+1)+L(L+1)]1/2

Dr. Usama El-Ayaan


mS = [4S(S+1)]1/2


The orbital contribution is usually quenched out by interaction with the electric fields of the ligands in its
environment.

mS = [n(n+2)]1/2

)Gd3+ (f7), Lu3+ (f14

Dr. Usama El-Ayaan


)(S
( (4f )(L

4f
5s and 5p
The ground terms and levels for free ions can be obtained using Hund's rules.
For an ion 2s+1LJ

Example 1. Nd3+; 4f3

For f-electrons, l=3 so ml = 3,2,1,0,-1,-2 and -3.
)Electrons have s=1/2 so ms=+1/2 (up spin or ) and -1/2 (down spin
The lowest energy arrangement for f3 according to rules (i) and (ii) is then:
ml
-3

-2

-1

Dr. Usama El-Ayaan

S=1/2+1/2+1/2 =3/2

L = 3+2+1 = 6.

The term symbol is written as 2S+1L where L is a label for the orbital angular
momentum according to the historical key:

J = L-S (n<7)
J = L+S (n>7)

L=

label

The ground term for Nd3+ is thus 4I9/2.

Dr. Usama El-Ayaan

Example 2
Pr3+ [Xe]4f2

Find Ground State from Hund's Rules

Maximum Multiplicity

S = 1/2 + 1/2 = 1

Maximum Orbital Angular Momentum

2S + 1 = 3

L=3+2=5

H state

Total Angular Momentum J = L-S = 5-1 = 4

3H
4
J = L-S (n<7)
J = L+S (n>7)

label S

L=

Dr. Usama El-Ayaan

config.

Ground

No. of

Ln

Ln3+

State

unpaired e-

Colour

La

4f0

S0

colourless

Ce

4f1

2F

5/2

colourless

2.54

2.3 - 2.5

Pr

4f2

H4

green

3.58

3.4 - 3.6

Nd

4f3

I9/2

lilac

3.62

3.5 - 3.6

Pm

4f4

I4

pink

2.68

Sm

4f5

H5/2

yellow

0.85

1.4 - 1.7

Eu

4f6

F0

pale pink

3.3 - 3.5

Gd

4f7

S7/2

colourless

7.94

7.9 - 8.0

Tb

4f8

F6

pale pink

9.72

9.5 - 9.8

Dy

4f9

H15/2

yellow

10.65

10.4 - 10.6

Ho

4f10

I8

yellow

10.6

10.4 - 10.7

Er

4f11

I15/2

rose-pink

9.58

9.4 - 9.6

Tm

4f12

H6

pale green

7.56

7.1 - 7.6

Yb

4f13

F7/2

colourless

4.54

4.3 - 4.9

Lu

4f14

colourless

7
6

S0

Dr. Usama El-Ayaan

Calculated

Observed

meff/mB

 - Ln3+

S +L

S only

Calculated values
Dr. Usama El-Ayaan

Dr. Usama El-Ayaan

Why not ?

SmIII and EuIII

Land formula fits well with observed

magnetic moments for all but SmIII and
EuIII
Moments of SmIII and EuIII are altered from
the Land expression by temperaturedependent population of low-lying excited
J-state(s)

Dr. Usama El-Ayaan

Why not ?

SmIII and EuIII

calculated values (Land formula ) show good

general agreement with experimental apart
from for Sm3+ and Eu3+.

both ions (Sm3+ and Eu3+) have excited

states close in energy to the ground term to
be thermally accessible and contribute to
the observed magnetic moment.
Dr. Usama El-Ayaan