QUANTUM MECHANICAL SPIN

(Dr. Cyriac Mathew)

The Postulate of spin:

In 1925, Uhlenbeck and Goudsmit, while studying the fine structure of D-line in the spectrum of sodium,
proposed that the electron has an intrinsic (in-built) angular momentum in addition to the orbital angular
momentum due to its motion about the nucleus. If we assume the electron as a sphere of charge spinning on its
own axis we can assume a charge loop on the surface that will give rise to an intrinsic angular momentum. This
angular momentum is termed as the spin angular momentum or, more simply, spin. However, electron spin has no
classical counterpart and the picture of an electron spinning on its own axis has no physical reality. But intrinsic
angular momentum is real even though there is no visualizable model available to explain its origin properly. We
know that each physical property has its own corresponding linear Hermitian Operator in quantum mechanics. These
operators can be constructed from the classical expression of the property by replacing p x, py, pz by appropriate
operators. Since the inherent spin angular momentum of a microscopic particle has no analog in classical mechanics,
we cannot use the above method to construct operators for spin. Therefore we simply use symbols for the spin
operators without giving an explicit form for them.
Analogous to the orbital-angular momentum operators L2 , L x , L y , Lz , we have the spin-angular momentum
operators S 2 , Sx , S y , Sz , which are postulated to be linear and Hermitian. S 2 is the operator for the square of the
magnitude of the total spin angular momentum of a particle. S z is the operator for the z component of the particles
spin angular momentum. We have, S 2 Sx2 S y2 Sz2 . We also postulate that the spin angular momentum
operators obey the same commutation relations as the orbital angular momentum operators. Analogous to

S x , S y i Sz , S y , Sz i S x , Sz , S x i S y . It can

Sx , S y , Sz , such that S 2 , S x S 2 , S y S 2 , Sz 0 .
2
Again the eigenvalues of S 2 can be shown to be s( s 1) with s = 0, , 1, 3/2, .., and that of S z be ms where
L x , L y i Lz , L y , Lz i L x , L z , L x i L y , we have

be shown that S 2 commute with any of the components,

ms = -s, -s+1, ,s 1, s. The quantum number s is called spin of the particle. For electrons the spin is . Protons
and neutrons also have a spin of .
With s = , the magnitude of the spin
angular
momentum
for
electron
is

1 1
2 2 1

1
3 . Similarly with s = , the
2

mz = 1/2

possible eigenvalues of S z of an electron as 12

and

12 .The electron spin eigenfunctions that

corresponds to these S z eigenvalues are denoted

and . Thus we have,

Sz 12
Sz 12

mz =
-spin

1/2

-spin

Since S z commutes with S 2 we can take the eigenfunctions of S z to be eigenfunctions of S 2 also, hence with s = ,

S 2

3
4

S 2

3
4

The term spin up () and spin down () refers to ms = and ms = .

The Stern-Gerlach Experiment

The most vivid experimental illustration for the nature of quantization is the one first performed by Otto
Stern and Walter Gerlach (gir-lack) in 1921. This experiment clearly demonstrated that angular momenta (and the
associated magnetic moments) are quantized, and space quantization makes possible the physical separation of
atoms or molecules in different quantum states. It also furnished the evidence from which the existence of electron
spin was later deduced. The experiment could be done with atoms having either spin or orbital angular momentum.
Stern and Gerlach worked with silver atoms ([Kr]4d105s1), which have a spin of (the same as the electron) and zero
orbital angular momentum. (MJ = ML + MS. For Ag atom in ground state L = 0 (S state) and ML = 0, S = and MS = MJ =
). The Silver atoms have a single unpaired electron that has an intrinsic magnetic moment. Hence each silver
atom has a magnetic moment associated with it and behaves, classically, like a tiny bar magnet (magnetic dipole)
even though such an analogy is incorrect.
The Stern-Gerlach experiment consists of passing a beam of silver atoms into an inhomogeneous magnetic
field, whose field strength is greater on one side of the beam than on the other. An atomic beam of silver atoms can
be made in a vacuum system by heating solid silver in an oven to a temperature at which the vapour pressure of the
silver is in the range of 102 torr. Allowing the atoms to escape through a series of collimating apertures in the wall of
the oven results in a beam of silver atoms, all travelling in the same direction, which is chosen to be the y-direction.
This beam of silver atoms, having well-defined direction, is then passed through a magnetic field that has a constant
value in the x-y plane and varies linearly with the z-coordinate, which is chosen to be perpendicular to the path of
the atoms. Such a field is generated using an inhomogeneous magnetic field as shown in the figure.

N
Ag

Ag
S

Classical picture of the Ag atom with the single

5s electron in two different orientations of its
spin angular momentum.

S
N

Oven

N
Screen

Screen 1

Screen 2

An inhomogeneous magnetic field will split the beam into its space-quantized (2J+1) components. It also exerts a
translational force and thus spatially separates the magnetic dipoles that are oriented differently. A homogeneous
magnetic field will orient magnetic dipoles but do not exert translational force and hence will not be able to separate
magnetic dipoles.
The magnetic field as shown in the above figure is stronger towards the south pole of the magnet. Any
particle entering the region of the field with its own south pole towards the south pole of the field is thus repelled

more by south-south repulsion than by north-north repulsion, and is driven towards the north pole. Similarly any
particle entering the field with its own north pole towards the fields south pole is driven towards South Pole of the
field. The extent of deflection depends on the field gradient.
If the atomic magnets were classical particles, their moments could initially be directed at any angle to the
field. One would then observe a continuous and symmetrical distribution of deflected atoms leaving the region of
the inhomogeneous field; some would be deflected towards fields north pole, some towards south pole, and some
would be undeflected. This situation is shown in screen 2, where there would not be any space-quantization. But
what actually observed is that one group of atoms all deflected the same amount toward the south pole and an
equal number deflected the same amount towards the north pole. The distribution is discontinuous (screen 1). This
is because the spin moments are not randomly oriented. If the applied field vector defines the z-axis then for S =
the z-component of magnetic moment can orient only in two distinct ways, . Atoms in each state are deflected
by a characteristic fixed amount, and the two distinct beams leaves the region of the field, each of these beam
contains only one spin state. The two spin states arise because of the two spin states of the single 5s electron of the
Ag atom. A schematic representation of the above experiment is shown below.

z
y
x

N
Since we have detected two beams of equal magnitude the quantum mechanical operator for measuring the
z-component of magnetic moment has only two eigenfunctions with eigenvalues that are equal in magnitude but
opposite in sign. Let us denote the operator by A and the two eigenfunctions by and and assume that they are
normalized. Since the experiment showed only two deflection angles, we conclude that and forms a complete
set and any acceptable wavefunction can be written as a linear combination of and .
SPIN ORBITALS
As mentioned earlier, spin is strictly a non-classical concept. We use and as the spin eigenfunctions.
These eigenfunctions are assumed to be orthonormal. Formally it is written as,

d d 1
d d 0 , where is called spin variable. It is not a spatial variable and the integration
*

over exists formally so that we can define orthonormality. The spin variable has no classical analog. (Spin is
independent of spatial coordinates and hence d could not be used).
The complete wavefunction include spatial function and spin function. We postulate that the spatial and spin
parts of a wavefunction are independent of each other. So we write the complete wavefunction as:
(x,y,z,) = (x,y,z)() or (x,y,z)()
The complete one-electron wavefunction is called a spin orbital. Using hydrogen-like wavefunctions as specific
examples, the first two spin orbitals of hydrogen-like atom are:
1

(1,0,0,

1
)
2

z3 2
e zr

1

(1,0,0,

1
)
2

z3 2
e zr

Antisymmetric wavefunctions
Let us consider the ground state helium atom. The total wavefunction for both the electrons including spin
can be written as, (1,2) = 1s(1)1s(2), where 1s and 1s are the spin-orbitals for electron 1 and electron 2
respectively. Since electrons are indistinguishable we can equally write, (2,1) = 1s(2)1s(1). Therefore we take
the linear combination of the two equations,
1 = (1,2) + (2,1) = 1s(1)1s(2) + 1s(2)1s(1) and
2 = (1,2) (2,1) = 1s(1)1s(2) 1s(2)1s(1)
Both 1 and 2 describe state in which there are two indistinguishable electrons; one electron is in the spin orbital
1s and the other in 1s. Neither wavefunction specifies which electron is in each spin orbital. This is because
electrons are indistinguishable.
Both the wavefunctions 1 and 2 are acceptable wavefunctions for the ground state of helium atom,
but experimentally only the wavefunction 2 describe the ground state of helium atom. Here 2 has the property
that it changes sign when the two electrons are interchanged. That is,

2 (1, 2) (1, 2) (2,1) and

2 (2,1) (2,1) (1, 2) 2 (1, 2) or
2 (2,1) 2 (1, 2)
We say that 2(1,2) is antisymmetric under the interchange of the two electrons.
This can be stated in the form of a postulate: (Postulate 6) All electronic wavefunctions must be antisymmetric
under the interchange of two electrons. This postulate is called the Pauli Principle.
In general, (q2,q1,qn,) = (q1,q2,qn,). Particles requiring antisymmetric wavefunction such as electrons are
called fermions (half-integral spin - electrons protons etc), while particles requiring symmetric wavefunctions such
as pions, are called Bosons (integral spin photons, -particle etc.).
Let us imagine the value of when electrons 1 and 2 have the same coordinate. ie. x1 = x2, y1 = y2, z1=z2, ms1 = ms2.
Thus by putting q2 = q1 in the above equation we have,
(q1,q1,qn,) = (q1,q1,qn,)
(q1,q1,qn,) + (q1,q1,qn,) = 0 or 2 (q1,q1,qn,) = 0
Thus two electrons with the same spin has zero probability of being found at the same point in the three
dimensional space. Since is a continuous function the last equation means that the probability of finding two
electrons with the same spin close to each other in space is quite small.
The Pauli Exclusion Principle
To a very good approximation, the Hamiltonian does not contain spin terms, so the energy is unaffected by
the inclusion of spin factor in the ground state wavefunction. Spectroscopic and chemical experiments indicate that
in the case of ground state helium atom only one state is available. This result confirms the validity of Pauli Principle.
The antisymmetric character of the electronic wavefunction can be best represented by the use of a
determinant. Thus the ground state helium atom may be written as:

1 1s (1) (1) 1s (1) (1)

. The rows represent the same electron occupying different orbitals and
2 1s (2) (2) 1s (2) (2)

columns represent different electrons occupying the same wavefunction; the opposite also can be written. In
general the normalization constant is

1
where n is the order of the determinant.
n!

Upon expansion we have,

1
1s (1) (1) 1s (2) (2) 1s (2) (2) 1s (1) (1)
2

In the determinant form the exchange of two electron coordinates is equivalent to exchanging two columns of the
determinant and according to the property of the determinant this changes the sign of the determinant. If two
columns or two rows of the determinant are identical the determinant vanishes. This would indicate that no such

state exists. Thus no two electrons have the same spin-orbital. This principle is found to hold not only for electrons
but also for any particle with half-integral spin like protons, neutrons etc. (fermions).

1s (1) (1) 1s (1) (1)

0
1s (2) (2) 1s (2) (2)
On the other hand for helium ground state wavefunction we have the following result:

(1,2)

1 1s (1) (1) 1s (1) (1) exchange

1 1s (1) (1) 1s (1) (1)

(2,1)
column
2 1s (2) (2) 1s (2) (2)
2 1s (2) (2) 1s (2) (2)

A wavefunction expressed as a determinant is called Slater determinant. When a wavefunction is written as a Slater
determinant it is automatically made antisymmetric.
The functions like 1s (1) (1) are called spin orbitals. A spin orbital is the product of a one-electron space
orbital and a one-electron spin function. When the columns or rows of a determinant have the same expression for
the spin orbitals the wavefunction would vanish. This important observation leads to the Pauli Exclusion Principle. It
can be stated as, no two electrons can occupy the same spin-orbital. In other words no two electrons in an atom can
have the same values for all the four quantum numbers. (cf. Pauli Principle: the total wavefunction (including spin)
must be antisymmetric with respect interchange of any pair of electrons.
Problem: show that the probability of having three electrons in a 1s orbital is zero.