Identical particles

Bosons and fermions

Two-particle systems
( ) ( ) ( )
1 2
1 2
2 2
2 2
1 2 1 2 1 2
1 1
1 2 1 2 1 2
1 2 1 1 2 2
2
2
1 1
1
( , , ) depends on coordinates and spin variables of both particles
( , , , )
2 2
If particles do not interact ( , , , ) ( ) ( )
,
( )
2
t
H V t
m m
V t V V
V
m

= +
= +
=

r r
r r
r r r r
r r r r
r

( ) ( )
( ) ( )
1 1
2
2
2 2 2 2
1
( )
2
n n n
n n n
E
V E
m

+ =


r r
r r r

Identical particles
If, however, particles are indistinguishable then interchanging particles should not
produce any observable difference. This means that probability distribution
corresponding to any two-particle state must remain the same when we exchange
the particles. Mathematically speaking we can say that
1 2 2 1
1 2 2 1
( , ) ( , ) P P

= r r r r
Using connection between the probability density and the wave functions we can obtain
( ) ( )
1 2 2 1
1 2 2 1
, ,

= r r r r
It turns out that the choice of + or sign in this relation depends on the spin of
particles. Particles with integer spin, such as photons, W and Z0 bosons require
symmetric wave functions, while particles with half-integer spin such as electrons,
protons, neutrons, and others require an antisymmetric wave functions.
Coordinate and spin states of identical
particles
Symmetrization or antysimmetrization requirements apply to entire wave functions
including their spin dependence. If spin and coordinate variables can be separated
we can analyze consequences of these requirements for each of the variables
separately.
( ) ( ) ( )
1 2
1 2 1 2 1 2
, ,

= r r r r
In the case of fermions the antisymmetric wave function can be obtained by two
different ways:
( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
1 2 2 1
1 2 2 1
1 2 2 1 1 2 2 1
1 2 2 1 1 2 2 1
, , if
1. , , and
2. , , and




=
= =
= =
r r r r
r r r r
r r r r
Basis of single-particle states
Let us assume that we know all single particle states of our system.
These are stationary states a Schrdinger equation with omitted
interaction term. They form a basis in the space containing coordinates
of each particle.
( )
1 1
,
n
r
( ) ( )
1 1 2 2
, ,
n m
r r
basis in the space of the first particle
( )
2 2
, basis in the space of the second particle
n
r
We need to construct a basis in the space containing two-particle wave
functions. Each of single particle spaces contain 2N states (including spin). Thus
the two-particle state must have dimension 2Nx2N. We can form functions (spinors)
That form a set of 2Nx2N linearly independent orthonormal spinors, and can, therefore,
we considered as a basis for the two-particle state. If, however, the particles are
undistinguishable this basis spinors have to be properly symmetrizied. For fermions we
should have
( ) ( ) ( ) ( )
1 1 2 2 1 1 2 2
, , , ,
n m m n
r r r r
Non-interacting distinguishable
particles. Example.
In the case of particles in the infinite square one particle states are
2
0
2
( ) sin ;
n n
n
x x E E n
a a

= =


If particles are distinguishable, the two particle states are
( )
2 2
1 2 0
1 2
2
( ) sin sin ;
2
( ) sin sin
nm n
nm
n m
x x x E E n m
a a a
n m
x x x
a a a

= = +



=


Ground state corresponds to n=m=1
0
2 E E =
The first excited state is double degenerate with n=1, m=2, and n=2, m=1 giving the
same energy
Non-interacting fermions in an
infinite square well.
Now the two-particle functions have to be made antisymmetric (we are
ignoring spin for now:
( )
1 2 1 2
2 2
0
2 1
( ) sin sin sin sin ;
2
nm
nm
n m m n
x x x x x
a a a a a
E E n m

=



= +
States with n=m=1 do not exist in this system. The lowest energy state will
correspond to n=1, m=2
12 1 2 1 2
0
2 1 2 2
( ) sin sin sin sin
2
5
x x x x x
a a a a a
E E

=



=
Non-interacting bosons in an
infinite square well.
Now the two-particle functions have to be made symmetric
( )
1 2 1 2
2 2
0
2 1
( ) sin sin sin sin ;
2
nm
nm
n m m n
x x x x x
a a a a a
E E n m

= +



= +
Ground state is the same as for distinguishable particles, but the next state
is no longer degenerate because n=1, m=2 and n=2, m=1 give the same
wave function
12 1 2 1 2
0
2 2 2
( ) sin sin sin sin
5
x x x x x
a a a a a
E E

= +



=
Singlet states
Now, let us take spin into account. Assuming again that coordinate and
spin variables can be separated we have for non-symmetric basis
functions
( ) ( )
1 2
1 2
(1) (2)
n m
r r
In the case of fermions we have two possibilities. First, the coordinate
wave function is symmetric, and spinor is antisymmetric:
( ) ( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
1 2 1 2
1 2 1 2
1 2 1 2
1
(1) (2) (1) (2)
2
1
00
2
1
2
n m m n
n m m n
n m m n




+ =

+ =

+

r r r r
r r r r
r r r r
This corresponds to a singlet
state of two spins, in which total
spin of two fermions is zero.
Triplet states
Second possibility is antisymmetric coordinate function and symmetric
spin function. It is immediately seen that there three possibilities to form
symmetric spin functions:
( )
1
; ;
2
+
Which we immediately recognize as three states of a triplet configuration of two
spins. Thus we can present the total wave function as
( ) ( ) ( ) ( )
1 2 1 2
1
1 ; 1,0,1
2
( , ) 0 Pauli exclusion principle
n m m n s s
m m
P
=

=
r r r r
r r
Exchange correlations
The symmetry requirements in the case of fermions and bosons result in
specific quantum mechanical correlation between the two particles even in
the absence of any direct interaction between them. Consider probability to
find two electrons within the same region of space for the spatially
symmetric state (in spatially antisymmetric state this probability is zero):
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
( ) ( )
( ) ( )
*
1 2 1 2 1 2 1 2 1 2

1 2 2 1 1 2 2 1
1 2 2 1
2 2
1 1 1 2
1 2 2 1
0 0 0 0
2 2
1
( , )
4
( , )
2
s n m m n n m m n
s n m
n m
P
P



= + +





+


= =




r r r r r r r r r r
r r r r
r r


This probability is twice larger than in the case of
distinguishable particles.
Exchange correlations and
interaction energy
Consider two interacting electrons. Their classical interaction energy is a
positive quantity (Coulomb repulsion). Quantum mechanical energy would
involve integration of the Coulomb term with the square of the respective
two-electron wave function, which we, of course, do not know.
Qualitatively, however, we understand, now that this wave function would
depend on the spin state of the electrons. In the triplet configuration
exchange correlations cause electrons to avoid each other: wave
functions goes to zero, when electrons approach each other. In the singlet
configuration exchange correlations favor electrons being closer to each
other. Thus we can say, that the exchange correlations imitate an
attractive potential for singlet thus lowering the energy of the system, and
they imitate an additional repulsive potential for triplet state increasing the
energy. We can conclude, therefore, that the energy of two interacting
spins depends on their spin state with lower energy corresponding to the
singlet state.
Exchange correlations and
chemical bonds
Consider now two hydrogen atoms in their ground state. When they are
far away from each other the electron wave functions do not overlap and
exchange contribution to energy is zero.
When they approach each other we have to distinguish
between electrons in triplet and singlet states.
In the singlet state (a) electrons tend to be closer to each other thus pushing
protons toward each other and keeping them together. This is howcovalent bond
arises. In one of the triplet states electrons avoid each other thus pushing protons
away from each other resulting in an anti-bonding state.
Atoms
2 2 2
2
1
0 0
1 1 1
2 4 24
Z Z
j
j j k
j
j k
Ze e
H
m r
r r

=


= +

Wave functions of electrons in a many-electron atom are stationary

states of the Hamiltonian below.
Because of the interaction term find these wave functions exactly is not
possible. In the first approximation we can neglect the interaction terms
and find single electron states, and then use them to calculate average
energy of the total Hamiltonian, hoping that it would give at least some
idea about the energy of the respective states. The multi-electron states
are formed as appropriately symmetrized products of single electron
states. They are characterized by single electron quantum numbers
n,l,m and by the spin state m
s
. One particle states are called orbitals.
Orbitals with the same n form a shell. Horizontal rows in Periodic Table
correspond to filling out each shell.
Z=1 through 10
2 1
means 0; means 1;
means 2; means 3
Capital , , , refer to the
total orbital moments of all electrons
S here means total spin,
designates grand
total momentum ( )
S
J
s l p l
d l f l
S P D F
L
J
L S
+
= =
= =
+
( ) ( ) ( )
2 2 2
100 200 210 21 1 211
1 2 2 2 2 2( )
2 electrons with 1 2,1,0
4 electrons with 0, spin state of 2 electrons can be either 1, or 0
can be 3,2,1,0. Actual state corresponds to 1, 0,
s s p a b c
l L
S S S
J L J S

+ + + +
= =
= = =
= = =1
Z=11 through 30
Hunds rules:
1. The state with the highest total S
have the lowest energy
2. For a given spin configuration,
the state with highest L
consistent with overall
antisymmetrization has lowest
energy
3. If a subshell (n,l) is no more than
half-filed, then J=L-S, otherwise,
it is J=L+S