Exercises Sheet 12

Prof. R. Grange Physics III, HS 2023

Handout: 8th December 2023

Submission: 19th December 2023

1 Commutation relations of spin operators

Learning Objective: Spin operators, Pauli matrices

Use the denitions of the Pauli matrices
     
0 1 0 −i 1 0
σx = σy = σz = (1)
1 0 i 0 0 −1

to compute the commutation relations of spin operators si = ℏ2 σi

a) Compute the commutation relation [si , sj ].
 2 
b) Compute the commutation relation s , si .
c) What do these results remind you of ? Make a link to what you already know from orbital
angular momentum operators.

d) Suppose a spin-1/2 particle is in the state

 
1 1+i
χ= √ . (2)
6 2

What are the probabilities of getting +ℏ/2 and −ℏ/2, if you measure ŝz ?

Solution
a) It is useful to compute all σi σj products to get used to some of the useful properties of Pauli
matrices:
    
0 1 0 −i i 0
σx σy = = = iσz
1 0 i 0 0 −i
    
0 −i 0 1 −i 0
σy σx = = = −iσz
i 0 1 0 0 i
    
0 1 1 0 0 −1
σx σz = = = −iσy
1 0 0 −1 1 0
    
1 0 0 1 0 1
σz σx = = = iσy
0 −1 1 0 −1 0
    
0 −i 1 0 0 i
σy σz = = = iσx
i 0 0 −1 i 0
    
1 0 0 −i 0 −i
σz σy = = = −iσx . (3)
0 −1 i 0 −i 0

ℏ
From this, together with si = 2 we can compute

ℏ2 ℏ2
[sx , sy ] = (σx σy − σy σx ) = 2iσz = ℏisz , (4)
4 4
ℏ2 ℏ2
[sy , sz ] = (σy σz − σz σy ) = 2iσx = ℏisx , (5)
4 4
ℏ2 ℏ2
[sz , sx ] = (σz σx − σx σz ) = 2iσy = ℏisy . (6)
4 4
and the rest of the commutation relations follow from [si , sj ] = − [sj , si ].

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Exercises Sheet 12 Prof. R. Grange; HS 2023

b) It is straightforward to prove another interesting property of the Pauli matrices:

  σi2 =
1 0
. That means that σ 2 = σx2 + σy2 + σz2 is a multiple of the identity operator, which
0 1
leaves things unchanged. Hence:

 2 
σ , σi = 0 ⇒ s2 , si = 0.
 
(7)

c) The results are identical to those obtained for orbital angular momentum operators. That is
because spin is also an angular momentum operator.

d) The wavefunction can be expressed as a sum of the basis states

   
1 0
χ=a +b (8)
0 1
√ √
with the two coecients a = (1 + i)/ 6 and b = 2/ 6. Since the basis states are eigenfunc-
2
tions of ŝz , the probability to nd +ℏ/2 for ŝz is |a| = 1/3, and the probability of getting
2
−ℏ/2 is |b| = 2/3.

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Exercises Sheet 12 Prof. R. Grange; HS 2023

2 Sequence of Stern-Gerlach boxes

Learning Objective: Spin, Stern-Gerlach experiment

Consider a particle with spin, e.g. a silver atom as discussed in the lecture, that travels through
a Stern Gerlach box (SGB). While the particle might previously have been in an undened spin
state, the SGB performs a measurement along its axis, say the z -axis, and projects the spin onto
one of the eigenstates in the z -direction. These states we denote in vector notation by
   
1 0
|↑z ⟩ = |↓z ⟩ = . (9)
0 1

We know that they are eigenvectors of the Pauli spin matrix σ̂z with eigenvalues ±1, respectively.
Say after passing this rst SGB, the particle is in state |ψ1 ⟩ = |↑z ⟩. In its path, we place a second
SGB in x-direction and examine the eect of that.

a) As a precursor, note that we can write the eigenstates of

   
sin θ cos ϕ σ̂x
ũ · σ̂ ≡  sin θ sin ϕ  · σ̂y  , (10)
cos θ σ̂z

where ũ is a unit vector in an arbitrary direction (θ, ϕ), in the z -basis as

|↑u ⟩ = cos(θ/2) e−iϕ/2 |↑z ⟩ + sin(θ/2) eiϕ/2 |↓z ⟩ (11)

−iϕ/2 iϕ/2
|↓u ⟩ = − sin(θ/2) e |↑z ⟩ + cos(θ/2) e |↓z ⟩ . (12)

Write out |↑x ⟩ and |↓x ⟩ and show that they are eigenstates of σ̂x .
b) In the braket and matrix notation, for every ket |a⟩ there is a corresponding bra ⟨a| that is
the complex transpose of the ket. The scalar product is then dened as the matrix product
of the two, e.g.
 

a1
⟨a|a⟩ = a∗1 a∗2 (13)
a2
= a∗1 a1 + a∗2 a2 . (14)

In a measurement process, the probability for a state |ψ⟩ to be projected onto a state |ϕ⟩ is
given by

2
P (ϕ|ψ) = |⟨ϕ|ψ⟩| . (15)

Calculate the probability of nding the particle in state |ψ2 ⟩ = |↑x ⟩ after the second SGB if
it was in state |ψ1 ⟩ = |↑z ⟩ after the rst SGB.

c) Assuming the particle is indeed in state |ψ2 ⟩ after the second SGB, calculate the probability
for nding it in |ψ3 ⟩ = |↑z ⟩ after a third SGB in z -direction. One could think that since it
used to be in the eigenstate |↑z ⟩ with respect to the z -axis, the probability of nding it in
that state again should be 1. Why is this reasoning wrong?

Solution
a) For the x-direction, it is (θ = π/2, ϕ = 0), therefore

1
|↑x ⟩ = √ (|↑z ⟩ + |↓z ⟩) (16)
2
1
|↓x ⟩ = − √ (|↑z ⟩ − |↓z ⟩) . (17)
2

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Exercises Sheet 12 Prof. R. Grange; HS 2023

Letting the operator σˆx act on these states we have

  √   √ 
0
1 +1/√2 +1/√2
σ̂x |↑x ⟩ = = = +1 |↑x ⟩ (18)
1
0 +1/ 2 +1/ 2
  √   √ 
0 1 −1/√2 +1/√2
σ̂x |↓x ⟩ = = = −1 |↓x ⟩ . (19)
1 0 +1/ 2 −1/ 2

So |↑x ⟩ and |↓x ⟩ are indeed eigenvectors of σ̂x with eigenvalues ±1.
b) In order to calculate the probability

2
P (↑x |ψ1 ) = |⟨↑x |ψ1 ⟩| , (20)

we can do this either exploiting orthonormality, namely

2
1
P (↑x |ψ1 ) = √ (⟨↑z | + ⟨↓z |) |↑z ⟩ (21)
2
2
1
= √ ⟨↑z | ↑z ⟩ + ⟨↓z | ↑z ⟩ (22)
2
1
= , (23)
2
or in the matrix notation as

  2
1
1 1
P (↑x |ψ1 ) = √ 1 1 = . (24)
2 0 2
1
So the probability of projecting an eigenstate of σ̂x onto an eigenstate of σ̂z is
2.

c) We can now easily do the next projection:

  2

1 1 1
P (↑z |ψ2 ) = P (↑z | ↑x ) = 1 0 √ = . (25)
2 1 2

Without the second SGB the reasoning in the statement would be sound because |↑z ⟩ would
be an eigenstate of the Hamiltonian in this case and therefore be a stationary state. So the
probability of nding it in this state should not change with time.

But since the second SGB projects the state onto another set of basis states, this is no
longer true. More generally, any quantum mechanical measurement inuences the system by
collapsing the wavefunction into an eigenstate of the measured observable.

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Exercises Sheet 12 Prof. R. Grange; HS 2023

3 Larmor precession

Learning Objective: Spin, magnetic elds

Consider a particle of spin 1/2 at rest in a uniform magnetic eld, which points in the z -direction.
The Hamiltonian for this system is
Ĥ = −γB0 ŝz (26)

a) What are the eigenstates of Ĥ ? What is the ground state energy?

b) Write down the general solutions of the time-independent Schrödinger equation for Ĥ .
c) The solution to the previous part b) should include two constant A and B which due to
2 2
normalization need to fulll |A| + |B| = 1. Therefore, we can write them without loss of
generality as
A = cos (α/2), B = sin (α/2). (27)

Using this, what is the expectation value of ŝx , ŝy and ŝz ?
d) Can you describe the orientation of the total spin ⟨ŝ⟩ as it evolves over time?

Solution
a) The eigenstates of Ĥ are those ofŝz , i.e. they are

 
1 γB0 ℏ
|↑⟩ = with energy E↑ = − (28)
0 2
 
0 γB0 ℏ
|↓⟩ = with energy E↓ = (29)
1 2

The energy is lowest for |↑⟩, i.e. when the dipole moment is parallel to the eld, as it would
be classically.

b) Since the Hamiltonian is time-independent, the general solution to the time-dependent Schrödinger
equation can be expressed in terms of the stationary eigenstates:

|χ(t)⟩ = Ae−iE↑ t/ℏ |↑⟩ + Be−iE↓ t/ℏ |↓⟩ (30)

c) As explained in the exercise, we can rewrite the coecients A and B with cos and sin. Thus
we can write |χ(t)⟩ as

|χ(t)⟩ = cos (α/2)e−iE↑ t/ℏ |↑⟩ + sin (α/2)e−iE↓ t/ℏ |↓⟩ . (31)

Now we can compute the expectation value of ŝx as

⟨ŝx ⟩ = ⟨χ(t)| ŝx |χ(t)⟩ (32)

cos (α/2)e−iE↑ t/ℏ

  

ℏ 0 1
= cos (α/2)eiE↑ t/ℏ sin (α/2)eiE↓ t/ℏ (33)
2 1 0 sin (α/2)e−iE↓ t/ℏ

sin (α/2)e−iE↓ t/ℏ
 
ℏ
= cos (α/2)eiE↑ t/ℏ sin (α/2)eiE↓ t/ℏ (34)
2 cos (α/2)e−iE↑ t/ℏ
ℏh i
= cos (α/2) sin (α/2)e−i(E↓ −E↑ )t/ℏ + cos (α/2) sin (α/2)ei(E↓ −E↑ )t/ℏ (35)
2
ℏ  
= cos (α/2) e−i(E↓ −E↑ )t/ℏ + ei(E↓ −E↑ )t/ℏ (36)
2
ℏ
= sin (α) cos (γB0 t) (37)
2

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Exercises Sheet 12 Prof. R. Grange; HS 2023

1 1
e−ix + eix


where we used sin(x) cos(x) = 2 sin (2x) and cos (x) = 2 and the denitions of
E↑/↓ in the last step.

For ŝy we nd very similarly:

⟨ŝy ⟩ = ⟨χ(t)| ŝy |χ(t)⟩ (38)

cos (α/2)e−iE↑ t/ℏ

  
iE t/ℏ iE t/ℏ

ℏ 0 −i
= cos (α/2)e ↑
sin (α/2)e ↓ (39)
2 i 0 sin (α/2)e−iE↓ t/ℏ

−i sin (α/2)e−iE↓ t/ℏ
 
ℏ iE t/ℏ iE t/ℏ
= cos (α/2)e ↑
sin (α/2)e ↓ (40)
2 i cos (α/2)e−iE↑ t/ℏ
ℏ h i
= cos (α/2) sin (α/2)(−i)e−i(E↓ −E↑ )t/ℏ + i cos (α/2) sin (α/2)ei(E↓ −E↑ )t/ℏ (41)
2
ℏ  
= − cos (α/2)i e−i(E↓ −E↑ )t/ℏ − ei(E↓ −E↑ )t/ℏ (42)
2
ℏ
= − sin (α) sin (γB0 t) (43)
2
1 −ix


where this time we used sin (x) =
2 e − eix in the last step.
Finally for ŝz we compute

⟨ŝz ⟩ = ⟨χ(t)| ŝz |χ(t)⟩ (44)

cos (α/2)e−iE↑ t/ℏ

  
iE↓ t/ℏ ℏ 1 0
iE↑ t/ℏ


= cos (α/2)e sin (α/2)e (45)
2 0 −1 sin (α/2)e−iE↓ t/ℏ

cos (α/2)e−iE↑ t/ℏ
 
ℏ iE↑ t/ℏ iE↓ t/ℏ
= cos (α/2)e sin (α/2)e (46)
2 − sin (α/2)e−iE↓ t/ℏ
ℏ 2
cos (α/2) − sin2 (α/2)

= (47)
2
ℏ
1 − sin2 (α/2) − sin2 (α/2)

= (48)
2
ℏ
= cos (α). (49)
2
where we used 1 − 2 sin2 (α/2) = cos (x).
d) ⟨⃗s⟩ is tilted at a constant angle α to the z -axis and rotates around this axis with the Larmor
frequency ω = γB0 . The situation is depicted in the following drawing:

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Exercises Sheet 12 Prof. R. Grange; HS 2023

4 Hydrogen states

Learning Objective: Hydrogen atom, spin, total angular momentum

The electron in a hydrogen atom occupies the combined spin and position state
p p 
R21 (r) 1/3Y10 χ↑ + 2/3Y11 χ↓ (50)

a) If you measured the orbital angular momentum squared ˆl2 , what values might you get, and
what ist the probability of each?

b) If you measured the z component of orbital angular momentum ˆlz , what values might you
get, and what is the probability of each?

c) If you measured the spin angular momentum squared ŝ2 , what values might you get, and
what is the probability of each?

d) If you measured the z component of spin angular momentum ŝz , what values might you get,
and what is the probability of each?

e) Let ĵ = ˆl + ŝ be the total angular momentum. If you measured ĵ 2 , what values might you
get?

f ) If you measured the position of the particle, what is the probability density for nding it at
r , θ , ϕ?
g) If you measured both the z component of the spin and the distance from the origin, what is
the probability per unit r for nding the particle with spin up and at radius r?
Hint: Note that [ŝz , r̂] = 0.

Solution
First it is useful to write down the possible values for all the quantum numbers of orbital and spin
angular momentum. From the form of the wavefunction we can immediately see that n=2 and
l = 1. For the quantum number m we need to notice that the electron is in a superposition of
states with m=0 and m = 1. Since the electron is a spin-1/2 particle, we have s = 1/2 and it is
again in a superposition of ms = +1/2 and ms = −1/2.
a) Since l = 1 for both terms, we know that l2 = ℏ2 l(l+1) = 2ℏ2 . Since there is no superposition
in this quantum number, the probability to nd this value is P (2ℏ2 ) = 1.
b) There are two possibilities according to the two possible quantum numbers and they are
given by mℏ. Their possibilities are given by the the modulus squared of the prefactor. Since
both the radial function
p p R21 (r) and the spin staets are normalized, they boil down to the
prefactors 1/3 and 2/3.
Thus a measurement will give lz = 0 with probability P (0) = 1/3 and lz = ℏ with probability
P (ℏ) = 2/3.
c) Since s = 1/2 for both terms, we know that s2 = 3ℏ2 /4 will be measured with certainty, i.e.
2
P (3ℏ /4) = 1.
d) For the z component of the spin angular momentum, there are again two possibilities accord-
ing to the two quantum numbers ms = ±1/2. Similarly to b) their probabilities are given by
the modulus squared ot the prefactor.

Thus we measure sz = +ℏ/2 with probability P (ℏ/2) = 1/3 and sz = −ℏ/2 with probability
P (−ℏ/2) = 2/3.
e) With the denition of ĵ we get an additional quantum number j for which |l − s| ≤ j ≤ l + s,
thus in the specic case j = 1/2, 3/2. The corresponding eigenvalues to the ĵ 2 operator are
j 2 = ℏ2 j(j + 1) thus we measure either j 2 = 3ℏ2 /4 or j 2 = 15ℏ2 /4.

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Exercises Sheet 12 Prof. R. Grange; HS 2023

Comment
To get the probabilities of these two outcomes one would need to either dive into a complicated
computation to get the expansion coecients of total angular momentum eigenstates in an
uncoupled tensor product basis. Typically these coecients are tabularized, they are called
Clebsch-gordan coecients .
1

f ) The probability of nding the particle at r, θ, ϕ is given by

2
2 2
p p
|ψ(r, θ, ϕ)| = |R21 (r)| 1/3Y10 (θ, ϕ)χ↑ + 2/3Y11 (θ, ϕ)χ↓ (51)

√
2 1 2 2 0∗
= |R21 (r)|  Y10 (θ, ϕ) χ†↑ χ↑ + Y1 (θ, ϕ)Y11 (θ, ϕ) χ†↑ χ↓ (52)
3 | {z } 3 | {z }
=1 =0

√
2 1∗ 2 2
+ Y1 (θ, ϕ)Y10 (θ, ϕ) χ†↓ χ↑ + Y11 (θ, ϕ) χ†↓ χ↓  (53)

3 | {z } 3 | {z }
=0 =1
 
2 1 0 2 2 2
= |R21 (r)| Y (θ, ϕ) + Y11 (θ, ϕ) (54)
3 1 3

From the analytic form of the spherical harmonics and the radial eigenfunctions (see for
example script section 6.2) we can rewrite this to

 
 2  2  2  2
2 1 r 1 3 2 3 2
|ψ(r, θ, ϕ)| = √ e−r/a0  √ cos2 (θ) + −√ sin2 (θ) eiϕ 
3(2a0 )3/2 a0 3 4π 3 8π | {z }
=1
(55)

9
r2 e−r/a0 cos2 (θ) + sin2 (θ)
 
= (56)
9 · 8a50 4π
1
= r2 e−r/a0 (57)
32πa50

g) If we measured the spin to be in the χ↑ the wavefunction collapses to the rst summand only.
Hence the probability to nd the electron at position r is

Z π Z 2π
2 1 0 2
P (r) = |R21 (r)| Y (θ, ϕ) r2 sin2 (θ)dθdϕ (58)
0 0 3 1

where we used χ†↑ χ↑ = 1 as in the previous part right away. Now we need to simplify
this integral, using the explicit form of the radial eigenfuction and the normalization of the
spherical harmonics:

1 1 4 −r/a
P (r) = r e ·1 (59)
3 24a5
1 4 −r/a0
= r e (60)
72a50

1 More information an be found here.

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Exercises Sheet 12 Prof. R. Grange; HS 2023

5 Spin and symmetry

Learning Objective: Spin, Multi-Electron wavefunctions, bosons and fermions

a) For a two electron atom like helium we can construct wavefunctions that are products of the
single electron wavefunctions, which for the ground state are

|Ψnlm , σ⟩ = |Ψ100 , ↑⟩ , |Ψ100 , ↓⟩ , (61)

and for the rst excited state are

|Ψnlm , σ⟩ = |Ψ200 , ↑⟩ , |Ψ200 , ↓⟩ . (62)

One possible product state of two electron ground state wavefunctions,

E
(1) (2)
Ψnlm Ψn′ l′ m′ , σ (1) σ ′(2) = |Ψnlm , σ⟩1 ⊗ |Ψn′ l′ m′ , σ ′ ⟩2 (63)

is E
(1) (2)
Ψ100 Ψ100 , ↑↓ = (|Ψ100 ⟩1 ⊗ |Ψ100 ⟩2 ) (|↑⟩1 ⊗ |↓⟩2 ) . (64)

Write down all possible product states of single electron ground state and rst excited state
wavefunctions.

b) Because electrons are identical particles, physical wavefunctions of two electron systems like
helium must be eigenstates of the exchange operator X̂ with eigenvalues ±1, where the
exchange operator has the following action,

E E
(1) (2) (1) (2)
X̂ Ψnlm Ψn′ l′ m′ , σ (1) σ (2) = Ψn′ l′ m′ Ψnlm , σ ′(1) σ (2) . (65)

Because spin commutes with the hydrogen Hamiltonian, all eigenstates must be able to
E
(1) (2)
factor into a spatial part Ψnlm Ψn′ l′ m′ and a spin part σ (1) σ (2) . Both parts must be

simultaneous eigenstates of X̂ . Find the 16 states that comprise the eigenbasis of X̂ by

taking linear combinations of the two electron product states. Write these states as products
of spatial and spin components.

c) In fact, electrons are fermions, so the eigenstates of helium must be those eigenstates of X̂
with eigenvalues −1 only. Identify these wavefunctions, and order them with respect to their
energies (taking into account the Coulomb repulsion term in the two-electron Hamiltonian).
Neglect any spin-dependence of the energy.

d) Imagine we had a very strange atom, where the electron was instead a bosonic particle with
spin 0. What would the wavefunctions of this strange bosonic form of helium be?

Solution
a) There are 4 dierent single electron states for the rst two energy levels, and these combine
into 16 possible two-electron product states:

E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ100 , ↑↑ , Ψ100 Ψ100 , ↑↓ , Ψ100 Ψ100 , ↓↑ , Ψ100 Ψ100 , ↓↓ ,
E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ200 , ↑↑ , Ψ100 Ψ200 , ↑↓ , Ψ100 Ψ200 , ↓↑ , Ψ100 Ψ200 , ↓↓ ,
E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ200 Ψ100 , ↑↑ , Ψ200 Ψ100 , ↑↓ , Ψ200 Ψ100 , ↓↑ , Ψ200 Ψ100 , ↓↓ ,
E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ200 Ψ200 , ↑↑ , Ψ200 Ψ200 , ↑↓ , Ψ200 Ψ200 , ↓↑ , Ψ200 Ψ200 , ↓↓ .

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Exercises Sheet 12 Prof. R. Grange; HS 2023

b) Of these 16 states we can see that 4 are symmetric under exchange, these must be eigenstates
of X̂ with eigenvalue +1,
E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ100 , ↑↑ , Ψ100 Ψ100 , ↓↓ , Ψ200 Ψ200 , ↑↑ , Ψ200 Ψ200 , ↓↓ .

There remain 6 more symmetric eigenstates, which we can form from superpositions of the
product states,

E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ100 , ↑↓ + Ψ100 Ψ100 , ↓↑ , Ψ200 Ψ200 , ↑↓ + Ψ200 Ψ200 , ↓↑ ,
E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ200 , ↑↑ + Ψ200 Ψ100 , ↑↑ , Ψ100 Ψ200 , ↓↓ + Ψ200 Ψ100 , ↓↓ ,
E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ200 , ↓↑ + Ψ200 Ψ100 , ↑↓ , Ψ100 Ψ200 , ↑↓ + Ψ200 Ψ100 , ↓↑ .

For the rst four of these we can easily factor the spatial part of wavefunction from the spin
part. The last two we can take the sum and dierence to create a new, but equally valid,
subspace,

E E
(1) (2) (1) (2)
Ψ100 Ψ100 (|↑↓⟩ + |↓↑⟩) , Ψ200 Ψ200 (|↑↓⟩ + |↓↑⟩) ,
 E E  E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ200 + Ψ200 Ψ100 |↑↑⟩ , Ψ100 Ψ200 + Ψ200 Ψ100 |↓↓⟩ ,
 E E  E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ200 + Ψ200 Ψ100 (|↓↑⟩ + |↑↓⟩) , Ψ100 Ψ200 − Ψ200 Ψ100 (|↓↑⟩ − |↑↓⟩) .

Even though this last wavefunction is the product of two antisymmetric wavefunctions, it is
overall symmetric.
Finally, there are 6 antisymmetric eigenstates of X̂ with eigenvalue −1 which we can form
from the antisymmetric superpositions of product states,

E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ100 , ↑↓ − Ψ100 Ψ100 , ↓↑ , Ψ200 Ψ200 , ↑↓ − Ψ200 Ψ200 , ↓↑ ,
E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ200 , ↑↑ − Ψ200 Ψ100 , ↑↑ , Ψ100 Ψ200 , ↓↓ − Ψ200 Ψ100 , ↓↓ ,
E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ200 , ↓↑ − Ψ200 Ψ100 , ↑↓ , Ψ100 Ψ200 , ↑↓ − Ψ200 Ψ100 , ↓↑ ,

which we can factor into spatial and spin parts like above,

E E
(1) (2) (1) (2)
Ψ100 Ψ100 (|↑↓⟩ − |↓↑⟩) , Ψ200 Ψ200 (|↑↓⟩ − |↓↑⟩) ,
 E E  E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ200 − Ψ200 Ψ100 |↑↑⟩ , Ψ100 Ψ200 − Ψ200 Ψ100 |↓↓⟩ ,
 E E  E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ200 − Ψ200 Ψ100 (|↓↑⟩ + |↑↓⟩) , Ψ100 Ψ200 + Ψ200 Ψ100 (|↓↑⟩ − |↑↓⟩) .

c) It is only the six antisymmetric wavefunctions identied above that can be helium eigenstates.
The energy of each state depends on the spatial part, because we neglected any terms in our
Hamiltonian that aect the spin. We will also assign a larger energy to symmetric spatial
wavefunctions compared to antisymmetric spatial wavefunctions because they are penalized
by the two-electron Coulomb repulsion term. The spatial wavefunctions ordered from lowest
energy to highest energy are:
E
(1) (2)
i) Ψ100 Ψ100
 E E
(1) (2) (1) (2)
ii) Ψ100 Ψ200 − Ψ200 Ψ100
 E E
(1) (2) (1) (2)
iii) Ψ100 Ψ200 + Ψ200 Ψ100
E
(1) (2)
iv) Ψ200 Ψ200

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Exercises Sheet 12 Prof. R. Grange; HS 2023

 E E
(1) (2) (1) (2)
where the three states with the antisymmetric wavefunction Ψ100 Ψ200 − Ψ200 Ψ100
form a degenerate spin-triplet.

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d) A spin-0 particle has exactly 1 spin eigenstate, compared to the two for the spin-
2 electron.
This means that we have only 4 possible two-particle product states,

E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ100 , Ψ100 Ψ200 , Ψ200 Ψ100 , Ψ200 Ψ200 .

Because the particles are bosons then the total wavefunction must be symmetric under ex-
change, so the following wavefunctions are allowed,

E E E E
(1) (2) (1) (2) (1) (2) (1) (2)
Ψ100 Ψ100 , Ψ100 Ψ200 + Ψ200 Ψ100 , Ψ200 Ψ200 .

There is one antisymmetric superposition that we can never nd this strange atom in,

E E
(1) (2) (1) (2)
Ψ100 Ψ200 − Ψ200 Ψ100 .

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