2.

Electron Spin

Contents

Electron spin angular momentum operator, eigenvalues and eigenfunctions;

hydrogen atom wavefunctions with electron spin; magnetic moment; magnetic
resonance.

Central Concepts
Spin (operator)

Difficult Points
Spin eigenfunctions which depend on no external parameters, but can be written in an
explicit way.

Notes

1. Spin Operators: Eigenvalues

The most important property for an angular momentum operator is

[i, j]=iijk k i,j,k=x,y,z. (1.1)

(See eq.(2.6) of Lecture 1) from which almost all other properties

can be derived. For the electron, the spin is just a form of angular
momentum, but it is intrinsic meaning it cannot be expressed into
the form like eqs.(2.1-3) or eqs.(2.15,22) of Lecture 1. However, we
can still find out the eigenvalues of the spin angular momentum
operators of the electron.

For convenience, we denote spin operators with S such as:

2= x2+ y2+ z2 (1.2)
Eq.(1) is just a compact form of the following equations:
[ x, y]=i z, [ y, z]=ix, [z, x]=i y, [ y, x]=-i z, etc. (1.1')
Similar to orbital angular momentum operators, we can easily obtain the following
equations:
 [2, x]=0, [2, y]=0, [2, z]=0 Or compactly, [2, i]=0, i=x,y,z (1.3)
Introducing ladder operators, we can find out the eigenvalues of . 2 and i
(i=x,y,z)
just by replacing L with S and repeating the procedure of Section 5.4 of the textbook.
The result is: the eigenvalues of 2 are
s(s+1) 2, s=0,1/2,1,3/2.(1.4)
and the eigenvalues of z are
ms, ms=-s,-s+1,,s-1,s. (1.5)
Figure: Illustration of the angular momentum vector for a tilted loop and its z
component Lz.

[If we change into , we get the same diagram for ANY angular
momentum.]

Generally, if the z-component of spin angular momentum is

measured to be mJ, the orientation of the total angular momentum
relative to z-direction is clearly
(. z)= cos-1(mJ/[J(J+1)]1/2) (1.6)
Therefore, if the z-component of spin angular momentum is
measured to be ms, the orientation of the total angular momentum
relative to z-direction is
(, z)=cos-1(ms/[s(s+1)]1/2) (1.6)
2. Electron Spin Operators: Eigenvalues and
Eigenfunctions
For electrons, experiment shows that the value of s is 1/2.[thus the
procedure in Section 5.4 can be made much simpler for electrons;
see textbook pp. 300-301: Because there are only two possible
 spin states, we clearly have +=0, +=,, -=, -=0
(2.1)

x=( ++-)/2= /2, x=( ++-)/2=/2 (2.2)

and
y=( +--)/2i= i/2, y=( +--)/2i=-i/2 (2.3)
These equations are usually expressed into matrix form as
x=0, x=/2, x=/2, x=0, (2.4a)
y=0, y=i/2, y=-i/2, y=0 (2.4b)
z=/2, z=0, z=0, z=-/2 (2.4c)
Can you write down the matrices x, y z? ]
Protons and neutrons also have s=1/2. Photons, the light
quantum have spin 1 (but there is no s=0 photons!!! Thats because
of relativistic effect for photons travel at the speed of light in the
vacuum.)
The total angular momentum of an electron is therefore
[s(s+1)]1/2 = [1/2(1/2+1)]1/2 =3/2 (2.5)
Applying eq.(1.5) to s=1/2 we have
z=/2 , z=-/2 (2.6)
Since commutes with z, the eigenfunctions of z can also be that
2

of 2 and we have
2=32/4, 2=32/4 (2.7)

Since there are only two possible spin states for electrons and they
depend no external variables as orbital angular momentum
eigenfunctions. However, we may write down the electron spin
eigenfunctions as follows

=(ms)=ms,1/2 , =(ms) ms,-1/2 (2.8)

[remember Diracs delta-functionms,1/2=1 if ms=1/2 or 0 otherwise]
and the normalization conditions can be readily obtained
ms=-1/2,ms=1/2|(ms)|2=1, ms=-1/2,ms=1/2|(ms)|2=1 (2.9)
[Proof: e.g., ms=-1/2,ms=1/2|(ms)|2=|0|2+|1|2=1]
and the orthogonality condition is
ms=-1/2,ms=1/2(ms)* (ms)=0 (2.10
ms=1/2 *
[proof: ms=-1/2, (ms) (ms)=0*1+1*0=0]

When both the space and spin variables are included, we have the following
normalization condition:
ms=-1/2,ms=1/2|(x,y,z,ms)|2dxdydz=1 (2.11
or equivalently
ms=-1/2,ms=1/2|(r,,,ms)|2 r2sindrdd=1 (2.12
[Note sometimes, the summation over ms is omitted and the above equations become
|(x,y,z,ms)|2dxdydz=1 and
|(r,,,ms)|2 r2sindrdd=1,respectively, but one should remember this summation
should always be performed whenever the normalization is carried out.]

3. Hydrogen Atom with Electron Spin

When the electron spin is considered, to a good approximation,

the Hamiltonian of hydrogen atom will be the same if there is no
magnetic field applied to it. Therefore the energy eigenequation will
be the same except the eigenfunctions are modified so that the spin
wavefunctions are taken into account:

nlm (r,) nlm (r,) g(ms) (3.1)

where g(ms) is the spin state which is generally a linear combination of and :
g(ms)=c1+c2. There are two independent choices for c1 and c2. Therefore, the
degeneracy of hydrogen atom eigenstate is changed into 2n2.

4. Magnetic Resonance

Associated with every spin S is a magnetic moment m:

m=gsqS/2m (4.1)
where m is the mass and q the charge of the spin and gs is g-factor. For electrons,
ge2, q=-e, we have
m=-eS/me|m|=-e|S|/me =-3e/2me (4.2)
Similarly, for protons, we have
m=geeS/2mp=3e/2mp (4.3)
When a spin is placed in a magnetic field, the energy is given by
E=-m B (4.4)
Above equation is the basis of all magnetic resonance spectroscopies such as ESR
(electron spin), NMR (nuclear spins), SR(muon spin) etc.
Suppose the magnetic field is along z-axis, we have
E=gsqmsB0/2m=msB0 (4.5)
where =gsq/2m is called gyromagnetic ratio which can either be positive or
negative depending on the sign of gs and q. The resonance frequencies then are found
to be given by
=E=B0(ms2-ms1) (4.6)
For single electrons and protons, there is only one frequency (B0). Because the mass
of proton is about 1840 times heavier than that of electron and the g factor of proton is
5.5857/2 times larger than that of electron, the proton NMR requency is
1840*2/5.5857700 times lower.

Summary

The electrons have an intrinsic angular momentum called spin. The spin operator
satisfies all the properties imposed on a quantum angular momentum operator and its
spin quantum number is 1/2 and it has the total angular momentum of 3/2. The
wavefunction of an atom/molecule must take the spin variable into consideration.
The spin is always related to a magnetic moment, which is the basis of ESR (electron
spin), NMR (nuclear spin), SR (muon spin) etc. The resonance frequency is
determined by the energy difference of the spins at different orientations in spin
space(eq.(4.6))

Questions

See assignment

Problems

See assignment

References

Textbook pp.282-285, pp.299-301.

Assignment
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