Intended Learning Outcomes of this lecture:

After this lecture you can

1. understand how the symmetry requirement on the spatial wavefunction leads to an
effective interaction or force.
2. describe the stability of a covalent bond using the symmetry properties of electrons.

Questions to start with:

Fermions: Pauli principle two non-interacting particles cannot occupy the same single-
particle state.
1. Is it repulsion in real space?
2. What about bosons?

Exchange Force another justification of repulsion between two non-interacting

identical particles if their combined spatial wavefunction is odd under exchange.

x2

x1

Qualitatively:

even
mean separation larger for odd
x1 x2
function tend to stay apart

odd

Analytically:
Suppose two non-interacting particles in two orthonormal states, a b = ab
Look at ( x1 x2 ) 2 = x12 + x22 2 x1 x2
Note: f = * f dx1dx2

PHYS3036 Spring 17 Ch. 5 Identical Particles (26/4/17) 1

Distinguishable
( x1 , x2 ) = a ( x1 ) b ( x2 )
x12 = a* ( x1 ) b* ( x2 ) x12 a ( x1 ) b ( x2 )dx1dx2

= b* ( x2 ) b ( x2 )dx2 a* ( x1 )x12 a ( x1 )dx1

= x2 a x2 a
a

x22 = x 2 b x2 b
b

x1 x2 = a* ( x1 ) b* ( x2 ) x1 x2 a ( x1 ) b ( x2 )dx1dx2
= a xa b xb
x a
x b

( x ) = x + x2 2 x
2 2
a
x b
a b

Indistinguishable
1
( x1 , x2 ) = [ a ( x1 ) b ( x2 ) a ( x2 ) b ( x1 )]
2
*
1 a ( x1 ) b ( x2 ) x1 a ( x1 ) b ( x2 )dx1dx2 a ( x1 ) b ( x2 ) x1 a ( x2 ) b ( x1 )dx1dx2
* 2 * * 2

x = 2
1
2 a* ( x2 ) b* ( x1 ) x12 a ( x1 ) b ( x2 )dx1dx2 + a* ( x2 ) b* ( x1 ) x12 a ( x2 ) b ( x1 )dx1dx2

1
= x2 + x2
2 a b

1
x22 = x 2 + x 2
2 b a

*
1 a ( x1 ) b ( x2 ) x1 x2 a ( x1 ) b ( x2 )dx1dx2 a ( x1 ) b ( x2 ) x1 x2 a ( x2 ) b ( x1 )dx1dx2
* * *

x1 x2 =
2 a* ( x2 ) b* ( x1 ) x1 x2 a ( x1 ) b ( x2 ) dx1dx2 + a* ( x2 ) b* ( x1 ) x1 x2 a ( x2 ) b ( x1 ) dx1dx2

1
= x a x b a x b b x a b x a a x b + x b x a
2
( x )
2
= x2 + x2 2 x a x b m 2 a x b
2

a
14444 b
24444 3 14243
same as distinguishable due to symmetry
particles requirement

if spatial wavefunction is
symmetric + : ( x )
2
smaller like a real space attraction
+

antisymmetric : ( x )
2
larger like a real space repulsion

PHYS3036 Spring 17 Ch. 5 Identical Particles (26/4/17) 2

Note: if

no overlap

x1 x2

| | =
= 0 as if they are distinguishable (we can distinguish
them not based on their intrinsic properties but in terms of their positions)
Interpretation: we need to worry about the indistinguishability of particles only when the
overlap of wavefunctions become significant.

In a covalent bond, e.g. HH, we know from high school chemistry that it is stable
because of electrostatic attraction:
electrostatic attraction

e-
+ e- +

high e density

Nave thinking: e are fermions, wave function is antisymmetric, real space repulsion
then why would e in a covalent bond stay close to each other? Something is missing!

We have missed out the ________________________

Total two-e wavefunction =

orbital (or spatial) spinor

means AND

PHYS3036 Spring 17 Ch. 5 Identical Particles (26/4/17) 3



symmetric (even) antisymmetric (odd)

antisymmetric antisymmetric (odd) symmetric (even)
1
Already know ( r1 , r2 ) = [ a (r1 ) b (r2 ) a ( r2 ) b ( r1 )]
2

What about spinors?

triplet, symmetric

1
2
( + )

1
2
( ) singlet, antisymmetric

Back to covalent bond

e-
+ e- +

e form singlet antisymmetric

symmetric
2 e close together
e in covalent bond always form singlet

PHYS3036 Spring 17 Ch. 5 Identical Particles (26/4/17) 4

Biography from Eric Weisstein's World of Science
http://scienceworld.wolfram.com/biography/

PHYS3036 Spring 17 Ch. 5 Identical Particles (26/4/17) 5