Recap: Last few days (1)

We showed how quantum mechanics describes identical particles

It does not distinguish between them

We introduced a new operator, the exchange operator, P12

where P12 f(1,2) = f(2,1)

We showed how this operator can be used to describe wavefunctions

that are either even or odd under the exchange of coordinates
describing particles
For identical particles, we saw [P12, H] =0. Non Degenerate EF of H
are also EF of P12

Recap: Last few days (2)

In cases where they were degenerate solutions, we could find a
linear combination of wavefunctions which were also solutions:
1
2

+ =
=

1
2

[n(x1) m(x2) + m(x1)n(x2)]

which is an even function

[n(x1) m(x2) m(x1)n(x2)]

which is an odd function

We described a more complete Hamiltonian for 1 electron atom by
introducing concepts
spin orbit coupling.
2 such as spin,
2
H (r , )

p
1 Ze

VSO r , .....smaller terms

2m 4 0 r

We introduced spin EF, S() = (),(). We said the full

wavefunction is given by

n r S

Recap: Last few days (3)

We saw that the quantum numbers (n, , m) determined the shape of
a wavefunction (as well as the energy).

The two electron atom

2

p1
p2
1
H 1,2 H (r1 , 1 , r2 , 2 )

2m 2m 4

Ze 2 Ze 2 e 2

r2
r12
r1

VSO (r1 , 1 ) VSO (r2 , 2 ) smaller terms

Electron 2

In short, we write

H (r1 , 1 , r2 , 2 ) H (1,2)

Electron 1

Recall the exchange operator, P12, interchanges all

coordinates (both orbital and spin of electrons 1 and 2)

We can separate the exchange operator in two parts. If

P12orb

is the exchange operator of the orbital coordinates, and if

P12spin

is the exchange operator of the spin coordinates, then

P12 P12orb P12spin

r12 r2 r1

r1

r2

Nucleus

p
p
1
H 1,2 H (r1 , 1 , r2 , 2 ) 1 2
2m 2m 4

Ze 2 Ze 2 e 2

r2
r12
r1

VSO (r1 , 1 ) VSO (r2 , 2 ) smaller terms

From the form of the Hamiltonian, we see that it is symmetric under
interchange of all coordinates of electrons 1 and 2.
Therefore

P12 , H 1,2 0

This implies that the EF of H(1,2) are either even or odd functions under
the exchange of coordinates.

To calculate the wavefunctions for the two electron atom,

We can simplify Hamiltonian, as follows:
Neglect the spin orbit and smaller terms
e 2 term, for the moment.
Neglect the (large!)

r12
The simplified Hamiltonian, now based only on spatial coordinates, looks like

p
p
1
H 0 r1 , r2 1 2
2m 2m 4 0

Ze 2 Ze 2

H 0 (r1 ) H 0 (r2 )

r2
r1

The solution is obtained from the solutions to the individual parts:

H 0 (r1 ) n (r1 ) E n0 n (r1 )

The EF of H 0 r1 , r2
and the EV is

and

H 0 (r2 ) m (r2 ) E m0 m (r2 )

are given by the product n ( r1 ) m (r2 )

0
E nm
E n0 E m0

Recall there is a case of degeneracy for a specific set of integers, nm, where
0
two distinct EF have energy E nm
.

1 n r1 m r2 and 2 m r1 n r2

These need not be EF of P12 but we can pick a linear combination which is an
EF of P12.

orb
orb
Lets consider P12 1 P12 n r1 m r2 m r1 n r2 2

Likewise

P12orb 2 1

So 1 and 2 are not EF of P12orb

But linear combinations of 1 and 2 are EF of P12orb and these are described by
1
1
1 2

1 2

and
2
2
where both states are degenerate and have energy E n+Em.

P12orb

and

P12orb

The spin description

To get the full wavefunction, we must multiply the orbital part by the appropriate spin
function.
The one electron spin functions are and . As we have not considered the effect of
spin on the energy, the energy of the state is not affected by which spin state the
electron is in.
So in the two electron atom we multiply the orbital state by the product of the spin
states, such as (1), (2), which indicates that that electron 1 is in the spin up
state, and electron 2 is in spin down state
There are four possible linearly independent spin functions
(1) (2)
(1) (2)
(1) (2)
(1) (2)

And as these have the same energy, we can pick linear combination of
the above spin functions.
The following linear combinations are particularly useful:
S 1 1 , 2 1 2

1
1 2 1 2
2
S 1 1 , 2 1 2

S 0 1 , 2

Since these are even under interchange

of spin coordinates, they are called S+
functions,
even EFs of P12spin
Further analysis shows that these three
states have a total Spin S=1.

1
1 2 1 2
S 1 , 2
2
0

Since this is odd under interchange

of spin coordinates, this is called a Sfunction. An odd EF of P12spin
Further analysis shows that this state
has a total Spin S=0.

The four spin states are orthonormal

The full wavefunction is a product of orbital and spin functions.

The two-electron wavefunction based on single electron n, m states is
+ * spin function (one of four above)
* spin function (one of four above)
Deeper analysis of these functions shows that:
S+ functions are EF of total spin and EV of total spin is 1, while the z components
of total spin (-1, 0, 1) in units of for states , respectively.
S- is an EF of total spin, with EV = 0; the z component is zero
S+ functions are spin triplets
S is a spin singlet
We can now consider the
following full wavefunctions:
Which are approximate EF of
the original Hamiltonian H(1,2).

r , r S ,
r , r S ,
r , r S ,
r1 , r2 S i 1 , 2

i 1, 0, 1
i 1, 0, 1


r , r S ,
r , r S ,
r , r S ,
r1 , r2 S i 1 , 2

i 1, 0, 1
i 1, 0, 1

We saw that H(1,2) commutes with P12 the operator which exchanges
the full coordinates (orbital & spin) of electrons 1 and 2.
The above eight wavefunctions are EF of P12.

P12 S P12orb P12spin S S S

Where +S+ and -S- are even under P12, while +S- and -S+ are odd
under P12.

Pauli Exclusion Principle

Based on experimental evidence, Pauli advanced the principle that the
wavefunctions for a system of electrons must be odd under the
exchange of all coordinates (orbital and spin) of any two electrons.
Mathematically we have seen that electronic wavefunctions can be
either even or odd;
Interpreting the Pauli Principle suggests that nature only requires odd
functions to describe electrons.

The Pauli Principle is an established principle of quantum physics.

It says that the wavefunction for a system of identical particles is
symmetrical under the interchange of all coordinates of any two
particles if they are of integral spin (particles, photons,
.BOSONS), while the wavefunction is antisymmetrical under
the interchange of all coordinates of any two identical particles if
the particles are of half integral spins (electrons, protons,
neutrons, mesons, .FERMIONS)
The name Bosons and Fermions refer to the fact that the particles obey
different statistical rules and these rules were worked out by Bose
and Einstein for integral spin particles and by Fermi and Dirac for
half-integral spin particles.

The Pauli Principle and two electron atom.

Returning to the two electron atom, we see the Pauli Principle restricts
the wavefunctions to antisymmetrical (odd) ones only.
The only valid wavefunctions are therefore +S- and -S+i.
And since the energy of + is above that of -, the energy levels are:

+S-

anti parallel spins (S=0)

2 H12
-S+i.

parallel spins (S=1)

The Coulomb repulsion between the electrons, allied with the Pauli Principle,
splits the two electron states into spin singlet (S=0) and spin triplets (S=1).

No two fermions can occupy the same state

Consider two electrons where the two spin orbit states are the same. That is the same
orbital quantum numbers apply (n, , m) describe the two states.
Consider the odd functions:
0
+S-: S 1 , 2

1
2

1 2 1 2 0 or

1
2

1 2 1 2 0

1 2 0
-S+i:
2

Consider the even orbital function is described by

n, , m r1 n, , m r2

If the two electrons have the same spin states, eg. Spin up, then the product of the
spin wavefunctions is the Even function (1) (2)=S+1, then the full spin orbital
S 1
is the even state
However by the Pauli Principle such an even spin orbital wavefunction is not
allowed.

Consequence of Pauli Principle

Thus we cannot have two electrons in the same orbital and spin states.
We can express this as follows:
In the same system, no two electrons can have the same quantum
number numbers (orbital and spin)
This is sometimes used as a simplified version of the Pauli Principle.