Lectures 5-6: Magnetic dipole moments

o Orbital dipole moments.

o Orbital precession.

o Spin-orbit interaction.

o Stern-Gerlach experiment.

o Total angular momentum.

o Fine structure, hyperfine structure of H and Na.

o Chapter 8 of Eisberg & Resnick

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 Sodium D-line doublet

o Grotrian diagram for doublet states of

neutral sodium showing permitted
transitions, including Na D-line
transition at 589 nm.

o D-line is split into a doublet:

D1 = 589.59 nm, D2 = 588.96 nm.

o Many lines of alkali atoms are doublets.

Occur because terms (bar s-term) are
split in two.

o This fine structure can only be Na D-line

understood via magnetic moments of
electron.

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 Orbital magnetic dipole moments

o Consider electron moving with velocity (v) in a circular Bohr orbit

of radius r. Produces a current l
e e
i
T 2
where T is the orbital period of the electron.
r
e-
o Current loop produces a magnetic field, with a moment v
L
e 2 1
l iA r er 2 (1)
2 2
o Specifies strength of magnetic dipole.

o Magnitude of orbital angular momentum is L = mvr = mr2.

Combining with Eqn. 1 => e
l L (2)
2m
o An electron in the first Bohr orbit with L has a magnetic
moment defined as
e
B = 9.27x10-24 Am2 Bohr Magneton
2m

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 Orbital magnetic dipole moments

o Magnetic moment can also be written in terms of the Bohr magneton:

gl B
l L

where gl is the orbital g-factor or Land g-factor. Gives ratio of magnetic moment to angular
momentum (in units of ).
gl B
o In vector form, Eqn 2 can be written
l L

gl B
o As L l(l 1) l l(l 1) gl B l(l 1)

o The components of the angular momentum in the z-direction are
Lz ml where ml = -l, -l +1, , 0, , +l - 1, +l.

o The magnetic moment associated with the z-component is correspondingly

gl B gl B
l
z
Lz ml gl B ml

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 Orbital precession

o When magnetic moments is placed in an external magnetic field, it experiences a torque:

l B
(3)
which tends to align dipole with the field. Potential energy associated with this force is
E B B
o Maximum potential energy occurs when l B.

o If E = const., l cannot align with
B => l precesses about B.
L Lsin
L sin (4)
t t
o From Eqn. 3,
gl B
l Bsin LBsin
equal to Eqn. 4 =>
o Setting this gl B
LBsin L sin
gl B
Larmor
B
frequency
o Called Larmor precession. Occurs in direction of B.

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 Electron spin

o Electron also has an intrinsic angular momentum, called spin. The

spin and its z-component obey identical relations to orbital AM:
S s(s 1)
Sz m s
where s = 1/2 is the spin quantum number => S 1/2(1/2 1)
3 /2
o orientations: Sz 1/2
Therefore two possible

=> spin magnetic quantum number is

1/2.

o Follows that electron has intrinsic magnetic moments: S
gsB

s S

s gsB ms
z

s
where gs (=2) is the spin g-factor.

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 The Stern-Gerlach experiment

o This experiment confirmed the quantisation of

electron spin into two orientations.

o Potential energy of electron spin magnetic

moment in magnetic field in z-direction is
s B sz B
E
gsB msB

o The resultant force is

d(E) dB
Fz B gsms z
dz dz

dBz
o As gsms = 1, Fz B
dz

o The deflection distance is then,

F L B L2 dBz
2

z 1/2at 1/2
2

m v 4KE dz

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 The Stern-Gerlach experiment

o Conclusion of Stern-Gerlach experiment:

o With field on, classically expect random distribution at target. In fact find two
bands as beam is split in two.

o There is directional quantisation, parallel or antiparallel to B.

o Atomic magnetic moment has z = B.

o Find same deflection for all atoms which have an s electron in the outermost
orbital => all angular momenta and magnetic moments of all inner electrons
cancel. Therefore only measure properties of outer s electron.

o The s electron has orbital angular momentum l = 0 => only observe spin.

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 The Stern-Gerlach experiment

o Experiment was confirmed using:

Element Electronic Configuration

H 1s1
Na {1s22s22p6}3s1
K {1s22s22p63s23p6}4s1
Cu {1s22s22p63s23p63d10}4s1
Ag {1s22s22p63s23p63d104s24p64d10}5s1
Cs {[Ag]5s25p6}6s1
Au {[Cs]5d104f14}6s1

o In all cases, l = 0 and s = 1/2.

o Note, shell penetration is not shown above.

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 Spin-orbit interaction

o Fine-structure in atomic spectra cannot be explained by Coulomb interaction

between nucleus and electron.

o Instead, must consider magnetic interaction between orbital magnetic moment and
the intrinsic spin magnetic moment.

o Called spin-orbit interaction.

o Weak in one-electron atoms, but strong in multi-electron atoms where total orbital
magnetic moment is large.

o Coupling of spin and orbital AM yields a total angular momentum, J.

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 Spin-orbit interaction
v
o Consider reference frame of electron: nucleus moves about
electron. Electron therefore in current loop which produces +Ze r -e
magnetic field. Charged nucleus moving with v produces a
current:
j Zev
o According to Amperes Law, this produces a magnetic field,
which at electron is

0 j r Ze0 v r
B
4 r 3 4 r3
Ze r -e
o Using Coulombs Law: E +Ze r
40 r 3
1
=> B 2 v E (5)
c v

where c 1/ 00

o is the magnetic field experienced by electron through E

This B
exerted on it by nucleus. j

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 Spin-orbit interaction

o s B
We know that the orientation potential energy of magnetic dipole moment is E

g g
s s B S E s B S B
but as

o Transforming back to reference frame with nucleus, must include the factor of 2 due to
Thomas precession (Appendix O of Eisberg & Resnick):

1 gsB
E so S B (6)
2
o This is the spin-orbit interaction energy.

o in terms of S and L. As force on electron is

More convenient to express
dV (r) r 1 dV (r) r
F eE E
dr r e dr r
can write Eqn. 5 as
1 1 dV (r)
B 2 v r
ec r dr

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 Spin-orbit interaction
1 1 dV (r)
o As L r mv mv r B L
emc 2 r dr
gsB 1 dV (r)
o Substituting the last expression for B into Eqn. 6 gives: E so S L
2emc 2 r dr
o 1 1 dV (r)
Evaluating gs and B, we obtain: E so S L
2m 2c 2 r dr
o For hydrogenic atoms, Ze 2 dV (r) Ze 2 General
V (r) form
4 0 r dr 4 0 r 2

1 1 Ze 2
o Substituting into equation for E: E so SL
2m 2c 2 r 4 0 r 2

e2 Z Hydrogenic
S L
4 0 c 2m cr
2 3
form
Z
E so 2 3
S L (7)
2m cr

o Expression for spin-orbit interaction in terms of L and S. Note, e 2 /40 c is the fine
structure constant.

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 Sodium fine structure

o Transition which gives rise to the Na D-line

doublet is 3p3s.

o 3p level is split into states with total angular

momentum j=3/2 and j=1/2, where j = l s.

o In the presence of additional externally magnetic

field, these levels are further split (Zeeman
effect).

o Magnitude of the spin-orbit interaction can be

calculated using Eqn. 7. In the case of the Na
doublet, difference in energy between the 3p3/2
and 3p1/2 sublevels is:

E = 0.0021 eV (or 0.597 nm)

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 Hydrogen fine structure

o Spectral lines of H found to be composed of

closely spaced doublets. Splitting is due to
interactions between electron spin S and the
orbital angular momentum L => spin-orbit
coupling.

o H line is single line according to the Bohr or

Schrdinger theory. Occurs at 656.47 nm for
H and 656.29 nm for D (isotope shift, ~0.2
H
nm).

o Spin-orbit coupling produces fine-structure

splitting of ~0.016 nm. Corresponds to an
internal magnetic field on the electron of
about 0.4 Tesla.

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 Total angular momentum

o Orbital and spin angular momenta couple together via the spin- z
orbit interaction.
S
J
o Internal magnetic field produces torque which results in
precession of L and S about their sum, the total angular
L
momentum:
J L S Vector model

L-S coupling of atom
o Called or Russell-Saunders coupling. Maintains
fixed magnitude and z-components, specified by two quantum
numbers j and mj:
J j( j 1)
Jz m j
where mj = -j, -j + 1, , +j - 1, +j.

o values of j? Must use vector inequality

But what are the

| L S ||| L | | S ||
| J ||| L | | S ||
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 Total angular momentum

o From the previous page, we can therefore write

j( j l) | l(l l) s(s l) |
o Since, s = 1/2, there are generally two members of series that satisfy this inequality:
j = l + 1/2, l - 1/2
o
For l = 0 => j = 1/2

o Some examples vector addition rules

o J = L + S, L = 3, S = 1
L + S = 4, |L - S| = 2, therefore J = 4, 3, 2.

o L = l1 + l2, l1 = 2, l2 = 0
l1 + l2 = 2, | l1 - l2 | = 2, therefore L = 2

o J = j1 + j2 , j1 = 5/2, j2 = 3/2
j1 + j2 = 4, | j1 - j2 | = 1, therefore J = 4, 3, 2, 1

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 Total angular momentum

o For multi-electron atoms where the spin-orbit

coupling is weak, it can be presumed that the
orbital angular momenta of the individual
electrons add to form a resultant orbital angular
momentum L.

o This kind of coupling is called L-S coupling or

Russell-Saunders coupling.

o Found to give good agreement with observed

spectral details for many light atoms.

o For heavier atoms, another coupling scheme

called j-j coupling provides better agreement
with experiment.

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 Total angular momentum in a magnetic field

o Total angular momentum can be visuallised as

precessing about any externally applied magnetic
field.

o Magnetic energy contribution is proportional Jz.

o Jz is quantized in values one unit apart, so for the

upper level of the sodium doublet with j=3/2, the
vector model gives the splitting in bottom figure.

o This treatment of the angular momentum is

appropriate for weak external magnetic fields where
the coupling between the spin and orbital angular
momenta can be presumed to be stronger than the
coupling to the external field.

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