3.

Pauli Principle

Contents
Identical particles, permutation symmetry, Pauli principle, Pauli repulsion, Pauli
exclusion principle, symmetric and antisymmetric wavefunctions, Fermion and
Boson, Slater determinants, permutation symmetry on electronic structure of atoms.
Central Concepts
Identical particles, permutation symmetry.
Difficult Points
Construction of proper wavefunctions for a given atomic/molecular system.

Notes
1. Permutation Symmetry of Identical Particles
Consider a system consisting a number of electrons which can access the same
volume of space. We call these electrons are identical. (However, if the electrons are
well separated in space, they are distinguishable because their spatial positions are
different.)
We may denote the electronic wavefunction as (q1,q2,q3.) with qi representing ALL
the parameters of the electron i. i.e. , qi =(ri,pi,msi). Obviously, since all electrons are
the same (identical), the wavefunction should reflect such a trivial fact that the
wavefunctions should give the same probability distribution of system if two (or
more) electrons i and j permute (exchange) their coordinates (qi is changed into qj
and vise versa), i.e.,
(qj,qi,qn.)=c(qi,qj,qn.)
where c is a non-zero constant.

(1.1)

Now we want to see what type of wavefunction can be selected as the candidate to
reflect the aforementioned fact, that is to say, what values the constant c may take.
Since permutation is an action that causes the wavefunction change, we can take the
permutation of the electrons as an operation just like any other operators. We may
rewrite eq.(1.1) as
Pij(qi,qj,qn.)(qj,qi,qn.)=c(qi,qj,qn.)

(1.2)

Then the task is to find out the eigenvalues of the permutation operator Pij.
Suppose that the eigenfunction of Pij. is w(qi,qj,qn.):
Pijw(qi,qj,qn.)=cw(qi,qj,qn.)

(1.3)

We notice that the repetition of applying Pij on the same eigenfunction returns it back
to its original state:
PijPijw(qi,qj,qn.)= Pijw(qj,qi,qn.)= w(qi,qj,qn.) (1.4)
but on the other hand, we have from the eq.(1.3) that PijPijw(qi,qj,qn.)=c2w(
qi,qj,qn.). (1.5)
Compare eqs.(1.4,5), we have c2=1 which means c=+1 or -1.
Thus we get the result: the wavefunction of a system of identical particles must satisfy
this condition: The permutation of the particles causes at most a sign change on the
wavefunction. We call the wavefunction symmetric if it upon permutation does not
change the sign and anti-symmetric if it does. In other words, only symmetric or antisymmetric wavefunctions are proper candidates for describing a system consisting of
identical particles.
2. Pauli Principle
According to above section, we can classify the identical systems into two categories:
one whose wavefunctions change sign after permutation (anti-symmetric) and the
other whose wavefunctions remain the same (symmetric) upon permutation.
Wolfgang Pauli found that fermions (particles with odd-half-integer spin quantum
numbers 1/2, 3/2, 5/2 etc) belong to the former while bosons (particles with integer
spin quantum numbers 0, 1, 2, ) belong to the latter. Because electrons are of spin1/2, it concludes that the wavefunctions of identical electrons must be anti-symmetric

That is called Pauli principle, as we listed as Postulate 6 of quantum mechanics

(Lecture 1). We see it is actually a special case of a more general conclusion (in fact,
it is a theorem of relativistic quantum field theory).
A simple consequence of the Pauli principle is that two electrons cannot stay at the
same place because(qi,qi,qn.)=- (qi,qi,qn.)=>
(qi,qi,qn.)=0. Namely, the anti-symmetric property of the wavefunction of
identical electrons keeps electrons apart as if there were repulsion between them. This
virtual repulsive force is called Pauli repulsion.
For a composite particle consisting of both fermions and bosons, the symmetry of its
wavefunction is determined by the number of fermions and bosons it contains. The
general form of the wavefunction can be written as (f1,fnf,b1.bnb) (nf and nb are
the number of fermions and bosons) which changes sign with every permutation on a
pair of fermions but does not change anything with permutations on bosons. If there
are an odd number of fermions, the composite is a fermion, otherwise, it is a boson.
Pauli principle offers a good simplification on the selection of wavefunctions for
electron systems in atoms and molecules: All wavefunctions that are not antisymmetric are ruled out.
The central task, therefore, is to construct the anti-symmetric wavefunctions from
the possible state functions. Generally, we have two independent spaces: ordinary
geometric space (r) and spin space (S). The total wavefunction can be written as the
direct product of the two wavefunctions in those two spaces. Therefore, we have two
possibilities: =r s where r is antisymmetric whiles is symmetric orr is
symmetric whiles is antisymmetric.
Example 1: Ground state of helium atom. It has two electrons. According to above
procedure, we first write the symmetric and anti-symmetric wavefunctions in spatial
and spin spaces, respectively, and then construct the anti-symmetric total
wavefucnions. However, in this case, the problem is simpler: we have only symmetric
spatial wavefunciton for helium ground state: 1s(1)1s(2). Therfore, we only ned to
find out the anti-symmetric spin states. All possible spin states are (1)(2), (1)(2),
(1)(2) and (1)(2). Clearly, the first and fourth are symmetric; the second and third
are neither symmetric nor anti-symmetric; none of above are anti-symmetric.
Therefore, we need to do some reconstruction job on the second and third states to get
the anti-symmetric spin states: i.e., find out proper linear combinations that are anti-

symmetric. The general linear combination is written as c1(1)(2)+c2(1)(2). So the

problem is find out proper c1 and c2. We first see what restriction is imposed on c1 and
c2 by normalization condition:
|c1(1)(2)+c2(1)(2)|2=1

(2.1)

which leads to
c1c1*+c2c2*=1

(2.2)

[Eq.(2.1) means [c1(1)(2)+c2(1)(2)] *[c1(1)(2)+c2(1)(2)]=1. By using the orthonomal

conditions on and : =1, =0, =0, =1, we readily come to eq.(2.2).]

If we apply permute 1 and 2, we get the state c2(1)(2)+c1(1)(2). In order to get

anti-symmetric result, we necessarily have
c1(1)(2)+c2(1)(2)=-(c2(1)(2)+c1(1)(2))

(2.3)

which means c1=-c2. From eq.(2.2), we have c1=1/2=-c2. Thus we get the antisymmetric spin states as
[(1)(2)-(1)(2)]/2

(2.4)

Since the two states in eq.(2.4) differ only by a sign, meaning they are equivalent,. We
may take either of them as the state function we need. Usually, we take the plus state.
Therefore, we get the correct ground state of helium atom:
1s(1)1s(2) [(1)(2)-(1)(2)]/2

(2.5)

which means that the two electrons have the same spatial wavefunction but have
opposite spin orientations. However, we must be careful about the exact meaning of
opposite orientationsit is an anti-symmetric combination of two basic spin states.
Example 2: First excited state of helium atom. Without considering spin variables, the
first excited state is the anti-symmetric combination of 1s and 2s (see Eq.(9.105) on
page 268 of the textbook): [1s(1)2s(2)-2s(1)1s(2)]/2. The spin states then have be
symmetric for the total wavefunctions to be anti-symmetric. The two possible
symmetric states were given before: (1)(2), (1)(2). The other one can be
constructed following the same procedure of eqs.(2.1-2.4) and it is
[(1)(2)+(1)(2)]/2. Therefore, the correct first excited states of helium atom are

(1)(2) [1s(1)2s(2)-2s(1)1s(2)]/2

(2.6a)

(1)(2) [1s(1)2s(2)-2s(1)1s(2)]/2

(2.6b)

[(1)(2)+(1)(2)][1s(1)2s(2)-2s(1)1s(2)]/2

(2.6c)

The next excited state of helium is

[(1)(2)-(1)(2)][1s(1)2s(2)+2s(1)1s(2)]/2

(2.7)

the combination of antisymmetric spin and symmetric spatial wavefunctions.

To a good approximation, the Hamiltonian does not contain spin terms, so the
energy is not affected by the inclusion of the spin factor. Only new degeneracy is
introduced. However, there do exist interactions involving spins as to be seen later.

3. Pauli Exclusion Principle

Now we turn to three electron systems such as lithium atom. We will see how
Paulis anti-symmetry principle imposes more striking restrictions on electronic states.
Suppose we have the spatial part of the ground state of lithium atom as
1s(1)1s(2)1s(3) which is symmetric. The spin state then has to be anti-symmetric.
How to construct an anti-symmetric wavefunction for a three-spin-1/2 system?
The answer is: impossible. How?
The proof is as follows: Suppose the basic states (for any variable, not only for
spin) of three identical particles are f, g and h. It is easy to find that there are six
possible permutations for three identical particles. The possible states are:
f(1)g(2)h(3), f(2)g(1)h(3), f(3)g(2)h(1), f(1)g(3)h(2), f(3)g(1)h(2) and f(2)g(3)h(1).
The general state of three identical particles can be written as the linear combination
of all possible product of the three states as follows:
c1f(1)g(2)h(3)+ c2f(2)g(1)h(3)+ c3f(3)g(2)h(1)+ c4f(1)g(3)h(2)+ c5f(3)g(1)h(2)+
c6f(2)g(3)h(1)
(3.1)
We wan to find the six coefficients c1 through c6 so that eq.(3.1) is anti-symmetric.
Suppose we exchange 1 with 2, we get

c1f(2)g(1)h(3)+ c2f(1)g(2)h(3)+ c3f(3)g(1)h(2)+ c4f(2)g(3)h(1)+ c5f(3)g(2)h(1)+

c6f(1)g(3)h(2)
(3.2)
The anti-symmetry demands that eq.(3.1) differs with eq.(3.2) by only a sign. Since
all six basic states are independent of each other That would mean the following
relations have to be satisfied:
c1=-c2, c3=-c5, c4=-c6

(3.3)

Similarly if we exchange 2 and 3, we get

c1f(3)g(2)h(1)+ c2f(2)g(3)h(1)+ c3f(1)g(2)h(3)+ c4f(3)g(1)h(2)+ c5f(1)g(3)h(2)+
c6f(2)g(1)h(3)
(3.4)
and the following relations
c1=-c3, c2=-c4, c5=-c6

(3.5)

Combining eqs.(3.3, 3.5), we have

c1=c4=c5=-c2=-c3=-c6

(3.6)

Therefore, the appropriate anti-symmetric wavefunction is of the form

c1[f(1)g(2)h(3)-f(2)g(1)h(3)-f(3)g(2)h(1)+f(1)g(3)h(2)+f(3)g(1)h(2)-f(2)g(3)h(1)
(3.7)
Using the orthonomality conditions for f, g and h, the normalization condition leads to
c1=1/6. Eq.(3.7) can be expressed as a determinant
f(1)
1/6

f(2)
f(3)

g(1)
g(2)
g(3)

h(1)
h(2)

(3.8)

h(3)

therefore, the acceptable wavefunction of a three-identical-particle-system is a threeorder determinant. For three spin-1/2-electron case, we have only two different
choices for f, g, h and eq.(3.8) becomes
(1)

(1)

(1)

1/6

(2)

(2)

(2)

(3)

(3)

(3)

(1)

(1)

(1)

(3.9a)

or

1/6

(2)
(3)

(2)
(3)

(2)

(3.9b)

(3)

It is easy to see both eqs.(3.9a, 3.9b) are zero because both have two identical
columns. [A determinant is zero if there are two identical columns or rows.]
Therefore, we have proved that the anti-symmetric spin state of a three-electron
system does not exist.
Eq.(3.8) has a famous effect on the electronic states in an atom. We consider both
the spatial and spin variables. Denote a spin orbital as 1s(i)(i) for i-th electron. It
instantly tells us from eq.(3.8) that it is not possible for two electrons occupy the
same spin orbital because the determinant would be zero if, for example, f=1s and
g=1s or g=1s and h=1s or f=1s, g=1s and h=1s. This is called Pauli
exclusion principle. We see Pauli exclusion principle is a special case of Pauli
principle.
For lithium atom, we see, it is impossible for three electrons to occupy 1s state. 2s
state has to be occupied. This is an example of the fact that there are very important
restrictions of the electron spin on atomic structure. According to eq.(3.8), we can
construct the following ground state for lithium atom:
1s(1)(1) 1s(1)(1) 2s(1)(1)
1/6 1s(2)(2) 1s(2)(2) 2s(2)(2)
1s(3)(3) 1s(3)(3) 2s(3)(3)

4. Slater Determinants

(3.10)

Eq.(3.8) can be extended to more general electronic systems. If ther are n electrons in
an atom, the general zero-th order ground state wavefunction can be written as a nthorder determinant, called the Salter determinant:
(0)(1,2,,i,..n)=
1(1) 2(1) i(1)n(1)
1(2) 2(2) i(2)n(2)
(4.1)

1/n! 1(i) 2(i) i(i)n(i)

1(n) 2(n) i(n)n(n)
where1,2i,n are the single particle states (spin orbitals). Eq.(3.11) may also be
written as a simplified form as (0)(1,2,,i,..n)=| 1,2,i,,n| where the two
vertical lines indicate the formation of determinant and the multiplication of the fact
1/n!.
For example, the ground state of helium atom is(0)(1,2)= |1,2|=|1s,1s| which
really means
(0)(1,2)=1/2
1s(1)(1) 1s(1)(1)
1s(2)(2) 1s(2)(2)
(4.2)
For excited states, the zero-th order wavefunction may be constructed with simple
linear combinations of the Slater determinants. Here simple means that the
coefficients in one combination differ at most by a sign. For example, it is
straightforward to verify that the excited state configuration 1s2s of helium atom
given by eqs.(2.6a,b,c,2.7) can be written as |1s,2s|, |1s,2s|, |1s,2s|+|
1s,2s|/2 and |1s,2s|-|1s,2s|/2,respectively.

5. Ground State Energy of Lithium Atom

In this section, we calculate the ground state energy of lithium atom with perturbation
theory and variation method, respectively.
The zero-th and perturbation Hamiltonians of lithium atom are
H(0)=-(21/2me)-(22/2me)-(23/2me)-Ze2/r1-Ze2/r2-Ze2/r3 (5.1)
H=e2/r12+e2/r23+e2/r13 (5.2)
5.1 Why 1s(1)1s(2)1s(3) cannot be the ground state of lithium atom?
First we prove that the configuration 1s(1)1s(2)1s(3) violates the variation pinciple
by evaluating its energy and comparing it with the experimental result. The zero-th
order energy would be for this state (eq.(9.48) in textbook: E(0)=-(1/n2+1/n2+1/n2)
(Z2e2/2a0) with n=1,Z=3):

E(0)=-(1/12+1/12+1/12)(Z2e2/2a0)=-27(e2/2a0)=-27(13.6eV)=-367.4 eV (5.3)
The first order energy correction is
E(1)=|1s(1)|2|1s(2)|2|1s(3)|2(e2/r12)dv+|1s(1)|2|1s(2)|2|1s(3)|2(e2/r23)dv+|1s(1)|
2
|1s(2)|2|1s(3)|2(e2/r13)dv
(5.4)
Because the symmetry of the indices 1, 2 and 3, above equation can be changed into
E(1)=|1s(1)|2|1s(2)|2|1s(3)|2(e2/r12)dv+|1s(3)|2|1s(2)|2|1s(1)|2(e2/r21)dv+|1s(1)|
2
|1s(3)|2|1s(2)|2(e2/r12)dv
(5.5)
All three integrals are the same, so we have
E(1)=3|1s(1)|2|1s(2)|2|1s(3)|2(e2/r12)dv
=3|1s(1)|2|1s(2)|2 (e2/r12)dv1dv2|1s(3)|2 dv3
=3|1s(1)|2|1s(2)|2 (e2/r12)dv1dv2=3(5Ze2/2a0)=153.1 eV (5.6)
Therefore the ground state energy is E(0)+E(1)=-214.3 eV where the experimental
result (by adding up the first, second and third ionization energies) is
(5.39+75.64+122.45) eV=-203.5 eV
which is larger than the theoretical result, violating the variation principle. Therefore,
the state 1s(1)1s(2)1s(3) cannot describe the correct ground state of lithium atom.
5.2 Perturbation treatment of lithium ground state
As we learned before, the correct ground state is given by eq.(3.10). Now we use
that zero-order ground state to calculate energy.
E(0)=-(1/12+1/12+1/22)(Z2e2/2a0)=-81(e2/2a0)/4=-81(13.6eV)/4=-275.5 eV (5.7)
To obtain the first order energy correction, we must calculate <(0)|H(1)|(0)> where
(0) and H(1) are given by eq.(3.10) and eq.(5.2), respectively. (0) can be expanded as
(0)=[1s(1)1s(2)2s(3)(1)(2)(3) 1s(1)2s(2)1s(3)(1)a(2)(3) - 1s(1)1s(2)2s(3)
(1)(2)(3)+ 1s(1)2s(2)2s(3)(1)(2)(3) + 2s(1)1s(2)1s(3)(1)(2)(3)
-2s(1)1s(2)1s(3) (1)(2)(3)]6-1/2 (5.7)
Which can be re-written as
(0)= 6-1/2[1s(1)2s(2)1s(3)-1s(1)1s(2)2s(3)] (1)(2)(3) + 6-1/2[1s(1)1s(2)2s(3)2s(1)1s(2)1s(3)] (1)(2)(3) + 6-1/2[2s(1)1s(2)1s(3)-1s(1)2s(2)1s(3)] (1)(2)(3)
=a(1)(2)(3)+ b(1)(2)(3) + c(1)(2)(3)=A+B+C (5.8)
a=6-1/2[1s(1)2s(2)1s(3)-1s(1)1s(2)2s(3)]

(5.9a)

b=6-1/2[1s(1)1s(2)2s(3)-2s(1)1s(2)1s(3)]

(5.9b)

c=6-1/2[2s(1)1s(2)1s(3)-1s(1)2s(2)1s(3)]

(5.9c)

The first order energy correction then is

E(1)=d(0)*H(0) (d=dv1dv2dv3)
=d(|A|2H+|B|2H+|C|2H+A*BH+B*CH+A*CH+AB*H+BC*H+AC*H) (5.10)
Because of the orthonomality conditions of the spin states, all integrals involving
cross terms A*B, B*C, A*C,AB*,BC*,AC* are zero (e.g., B*C= [b(1)(2)(3)] *
[ c(1)(2)(3)] = b*c*(1) (1)*(2) (2)*(3) (3)=0 since *(2) (2)=0 and also
*(3)(3)=0.) Thus, eq.(5.10) becomes
E(1) =dv1dv2dv3(|A|2H+|B|2H+|C|2H)=a2Hdv1dv2dv3
+b2Hdv1dv2dv3+b2Hdv1dv2dv3+dv1dv2dv3

(5.11)

Substituting the expressions of a, b, c into above equation and using the

orthonomality condition for 1s and 2s orbitals, we get:
E(1) =21s2(1)2s2(2)(e2/r12)dv1dv2+1s2(1)1s2(2)(e2/r12)dv1dv2-1s(1)2s(2) 1s(2)2s(1)
(e2/r12)dv1dv2 =2J1s2s+J1s1s-K1s2s (5.12)
We already had the values of J1s2s, J1s1s and K1s2s before (eqs.(9.52,9.55,9.113))
J1s2s= 5(Ze2/a0)/8, J1s1s=17(Ze2/a0)/81, K1s2s=16(Ze2/a0)/729

(5.13)

Finally, the first order energy correction is found to be E(1) =5965e2/a0)/972=83.5 eV.
The energy through the first order is therefore -275.5 eV+83.5 eV=-192.0 eV. It
does not violate variation principle although it is still not sufficiently accurate.
Higher- order corrections have to be included to further improve the accuracy.
5.2 Variation treatment of lithium ground state
According to Table 6.2 (textbook p.149), we use the following trial function as the 1s
state:
f=(b1/a0)3/2e-b r/a0/1/2
1

(5.14)

and the trial function for the 2s state:

g=(b2/a0)3/2(2-b2r/a0)e-b r/a0/4(2)1/2
2

(5.15)

The trial variation function for the ground state of lithium atom then is given by
=
f(1)(1) f(1)(1) g(1)(1)
1/6 f(2)(2) f(2)(2) g(2)(2)

(5.16)

f(3)(3) f(3)(3) g(3)(3)

(cf eq.(3.10). The energy correction is W=<|H|>. The best parameters found from
W/b1=0 and W/b2=0 are b1=2.686 and b2=1.776 and W=-201.2 eV which is
much better than the first order perturbation result. However, there is still some room
for further correction by, for example, introducing r12, r23, r13 into the trial function.

Summary
The fermionic properties of the electrons demand that the wavefunction must be antisymmetric. One important consequence of Pauli principle is that one spin orbital
cannot be occupied by two or more electrons. Anti-symmetric wavefunctions can be
constructed by making use of the Slater determinant.

Questions
See assignment

Problems
See assignment

Applications and Extended Readings/Exercises

References
Textbook pp.285-299. .

Assignment
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