Ch4 Fine structure of atoms

Magnetic moments
Spin of the electron
Stern-Gerlach experiment
Spectrum of the alkali atoms
Spin-orbit coupling (interaction)
The Zeeman effect
 Some words
Fine structure Spin-orbit coupling
Electron spin (interaction)
Orbital motion Frame of reference
Magnetic moment Larmor precession
Alkali atoms Lande g factor
Valence Alkali metals
intrinsic diffuse
Magneton Stern-Gerlach experiment
Atomic state Zeemans effect
Magnetic moment of the orbital
motion
An electron moving in an orbit is equivalent to
a circular current, which

possesses
e e
a magnetic
moment. l
B (Bohr magneton)
2m 2m
The magnetic moment associated with the
orbital angular momentum is quantised.
An applied magnetic field B acts on the orbital
magnetic moment by trying to align the vectors
l and B. The electrons precess about the
direction of the field, called Larmor precession.
There is also a potential energy E=- l B.
 Electron spin
Electron spin was introduced by Uhlenbeck and
Goudsmit in 1925. They proposed that the
electron possesses an intrinsic angular
momentum independent of any orbital angular
momentum it might have. Four quantum
numbers: n, l, ml, ms.
The splitting of many spectral lines in a magnetic
field can only be explained if the electron has a
spin angular momentum s.
e
| s | s ( s 1) s gS s
2m
The total angular momentum
& magnetic moment
j
l
j l s , l s
s
j l cos( j , l ) s cos( j , s )
g j J B
S

l

3 1 s 2 l 2
gj ( )
2 2 j 2 j
 Fine structure
All energy levels except the s states of one-
electron atoms are spit into two substates. This
produces a doublet or multiplet structure of the
spectral lines, namely, fine structure.
It can not be explained by Coulomb interaction
between the nucleus and the electrons. It results
from a magnetic interaction between the orbital
magnetic moment and spin magnetic moment
of the electron, called spin-orbit coupling.
 Spin-orbit coupling (I)
An electron revolving about a nucleus finds
itself in a magnetic field produced by the
nucleus which is circling about it in its own
frame of reference.
This magnetic field then acts upon the electrons
own spin magnetic moment to produce substates
in terms of energy. S=1/2 could make some
single state (n,l,m) split into two substates.

1 Ze 2
Vls S BNuc s l
4 0 2me c r
2 2 3

(Z ) 4 me c 2 [ j ( j 1) l (l 1) 34 ]

4n 3 l (l 12 )(l 1)
 Spin-orbit coupling (II)
The coupling of two magnetic moments in an atom
leads to an addition of the two angular momenta to
yield a total angular momentum. j=l+s
The total angular momentum has the magnitude of
with j=|l1/2| for a single electron system.
The quantum number j is the quantum number of
the total angular momentum
j ( j 1)
.
For a p electron, l=1, s=1/2, there are two states
with j=1/2, 3/2, respectively.
The symbolism for atomic states
The atomic state is denoted by a symbol, and
the orbital angular momentum is indicated by
upper case letters S,P,D,F.
The primary quantum number n is written as
an integer in front of the letter, and the total
angular momentum quantum number j as a
subscript.
The multiplicity 2s+1 (the number of j values)
is indicated by a superscript to the left of the
letter.
n 2 s 1l j 2 2P1/ 2 2 2P3 / 2 (n 1,l 1, j 1/ 2 , 3 / 2)
 Lande g factor
It is a measure of the ratio of the magnetic
moment (in Bohr magnetons) to the angular
momentum (in units of h bar).

For the orbit

j j ( angular
j 1) g
j B
momentum,
m g gj=l,
jz j j B j
j
g l=1. For
B

j ( j 1)
spin angular momentum, j=s, gs=2.
For the total angular momentum, g factor is
given by:
3 1 s 2 l 2
gj ( 2 )
2 2 j
 The alkali atoms
The alkali atoms have a weakly
bound outer electron, the so-
called valence electron, and all
other (Z-1) electrons are in
closed shells.
The yellow D line in the
spectrum of the sodium (Na)
atom, i.e. the transition
3P3S,is a doublet:
D1=589nm, D2=589.6nm.
 Alkali metals
Selection rules:
The first primary series: nP2S, P: double
lines
substates , doublet, two l are , j closer
1,getting 1,0
with n increased.
The sharp secondary series: nS2P, doublet, two
lines are separated uniformly with n increased.
The diffuse secondary series nD2P, are triplet, D
& P are both split into substates. 2D5/22P3/2,
2D 2P , 2 D 2P
1/2; D5/2 P1/2(?)
2 2
3/2 3/2 3/2
Spectrum of alkali metals

First primary series

Sharp secondary series

Diffuse secondary series

 Stern-Gerlach experiment (I)
Space quantization was first explicitly
demonstrated by Stern & Gerlach in 1921.
They directed a beam of neutral silver atoms from
an oven through a set of collimating slits into an
inhomogeneous magnetic field B which exerts a
force on the magnetic moments.
When the magnetic moment is parallel to B, it
moves in the direction of increasing field
strength, while an anti-parallel magnetic moment
moves towards lower field strength.
Stern-Gerlach experiment (II)
dB dB
Fz z m j g j B
dz dz
They found that the initial beam split into two
distinct parts which correspond to the two
opposite spin orientation in the magnetic
field.
For hydrogen atoms in ground state, n=1, l=0,
j=s, mj=-1/2, +1/2, gj=2, mjgj =1,
Stern-Gerlach apparatus
 The Zeeman effect
The total angular momentum J is the vector sum of
orbital angular momentum and spin angular
momentum. J=L+S

When there is noJ external

j ( j magnetic
1) J z field,the
m j total
angular momentum is conserved. When an external B is
applied, J precesses about the direction of B, causing
additional potential energy mgBB (2j+1 levels).
Selection rules:

m 0,1