FI-3103 Quantum Physics
Problem Set 11b
Chapter 11: The Real Hydrogen Atom (Part 2)
1. Calculate the energy spectrum of the 𝑛 = 2 states in the real hydrogen atom, ignoring
hyperfine structure. How is the spectrum changed when the atom is placed in a magnetic
field of 2.5 T?
2. Consider hydrogen gas in its ground state. What is the effect of a magnetic field on the
hyperfine structure? Calculate the spectrum for 𝐵 = 10−4 T and for 𝐵 = 1 T. Hint: To
solve this, set up an eigenvalue problem for the interaction
𝐴(𝐒 ⋅ 𝐈) 𝑆𝑧 𝐼𝑧
+ 𝑎 ( ) + 𝑏 ( )
ℏ2 ℏ ℏ
with
4𝑚𝑒 4 𝑒ℏ𝐵 𝑒𝑔𝑃 ℏ𝐵
𝐴 = 𝑔𝑃 ( ) 𝛼 𝑚𝑒 𝑐 2 ; 𝑎 = ;𝑏 = −
3𝑀𝑃 𝑚𝑒 2𝑀𝑃
3 2 2 2
3. Consider the transitions 3𝑃1 → 1𝑃1 ; 3𝑃3 → 1𝑆1 in hydrogenlike atoms.
2 2 2 2
a. Calculate the wavelengths of light emitted in these transitions as a function of 𝑍.
b. In sodium the wavelengths are 589.592 nm and588.995 nm respectively. What value
of 𝑍 does this correspond to?
4. The deuteron consist of a proton (charge +𝑒) and a neutron (charge 0) in a state of total
spin 1 and total angular momentum 𝐽 = 1. The 𝑔-factors for the proton and neutron are
𝑔𝑃 = 2(2.7896)
𝑔𝑁 = 2(−1.9103)
a. What are the possible orbital angular momentum states for this system? If it is known
that the state is primarily 𝑆13 , what admixtyre is allowed given that parity is conserved?
b. Write an expression for the interaction of the deuteron with an external magnetic field
and calculate the Zeeman splitting. Show that if the interaction with the magnetic field
is written in the form
𝑉 = −𝛍𝐞𝐟𝐟 ⋅ 𝐁
then the effective magnetic moment of the deuteron is the sum of the proton and
neutron magnetic moments, and any deviation from that result is due to an admixture
of non-𝑆 state to the wave function.
Solution
1. The effects that enter into the energy levels corresponding to 𝑛 = 2, are (i) the basic
Coulomb interaction, (ii) relativistic and spin-orbit effects, and (iii) the hyperfine structure
which we are instructed to ignore. Thus, in the absence of a magnetic field, the levels under
the influence of the Coulomb potential consist of 2𝑛2 = 8 degenerate levels. Two of the
levels are associated with 𝑙 = 0 (spin up and spin down) and six levels with 𝑙 = 1,
corresponding to 𝑚𝑙 = 1,0, −1, spin up and spin down. The latter can be rearranged into
1 1
states characterized by 𝐉 𝟐 , 𝐋𝟐 and 𝐽𝑧 . There are two levels characterized by 𝑗 = 𝑙 − =
2 2
1 3
and four levels with 𝑗 = 𝑙 + 2 = 2. These energies are split by relativistic effects and spin-
orbit coupling, as given in Eq. (12-16, Gaziorowicz). We ignore reduced mass effects (other
than in the original Coulomb energies). We therefore have
1 1 1 3
Δ𝐸 = − 𝑚𝑒 𝑐 2 𝛼 4 3 ( − )
2 𝑛 𝑗 + 1 4𝑛
2
1 5 1
= − 𝑚𝑒 𝑐 2 𝛼 4 ( ) 𝑗=
2 64 2
1 1 3
= − 𝑚𝑒 𝑐 2 𝛼 4 ( ) 𝑗=
2 64 2
The Zeeman splittings for a given 𝑗 are
𝑒ℏ𝐵 2 1
Δ𝐸𝐵 = 𝑚𝑗 ( ) 𝑗=
2𝑚𝑒 3 2
𝑒ℏ𝐵 4 3
= 𝑚𝑗 ( ) 𝑗=
2𝑚𝑒 3 2
1 𝑒ℏ𝐵
Numerically 𝑚𝑒 𝑐 2 𝛼 4 ≈ 1.132 × 10−5 eV, while for 𝐵 = 2.5 T, = 14.47 ×
128 2𝑚𝑒
10−5 eV, so under these circumstances the magnetic effect are a factor of 13 larger than the
relativistic effects. Under these circumstances one could neglect these and use Eq. (12-26,
Gaziorowicz).
2. The unperturbed Hamiltonian is given by Eq. (12-34, Gaziorowicz) and the magnetic field
interacts both with the spin of the electron and the spin of the proton. This leads to
𝐴(𝐒 ⋅ 𝐈) 𝑆𝑧 𝐼𝑧
𝐻= 2
+𝑎( )+𝑏( )
ℏ ℏ ℏ
Let us now introduce the total spin 𝐅 = 𝐒 + 𝐈. It follows that
𝐒⋅𝐈 1 3 3
2
= 2 (ℏ2 𝐹(𝐹 + 1) − ℏ2 − ℏ2 )
ℏ 2ℏ 4 4
1
= 𝐹=1
4
3
=− 𝐹=0
4
We next need to calculate the matrix elements of 𝑎𝑆𝑧 + 𝑏𝐼𝑧 for eigenstates of 𝐅 𝟐 and 𝐹𝑧 .
These will be exactly like the spin triplet and spin singlet eigenstates. These are
1
⟨1,1|𝑎𝑆𝑧 + 𝑏𝐼𝑧 |1,1⟩ = ⟨𝜒+ 𝜉+ |𝑎𝑆𝑧 + 𝑏𝐼𝑧 |𝜒+ 𝜉+ ⟩ = (𝑎 + 𝑏)
2
2
1
⟨1,0|𝑎𝑆𝑧 + 𝑏𝐼𝑧 |1,0⟩ = ( ) ⟨𝜒+ 𝜉− + 𝜒− 𝜉+ |𝑎𝑆𝑧 + 𝑏𝐼𝑧 |𝜒+ 𝜉− + 𝜒− 𝜉+ ⟩ = 0
√2
1
⟨1, −1|𝑎𝑆𝑧 + 𝑏𝐼𝑧 |1, −1⟩ = ⟨𝜒− 𝜉− |𝑎𝑆𝑧 + 𝑏𝐼𝑧 |𝜒− 𝜉− ⟩ = − (𝑎 + 𝑏)
2
And for the singlet state (𝐹 = 0)
1 2 1
⟨1,0|𝑎𝑆𝑧 + 𝑏𝐼𝑧 |0,0⟩ = ( ) ⟨𝜒+ 𝜉− + 𝜒− 𝜉+ |𝑎𝑆𝑧 + 𝑏𝐼𝑧 |𝜒+ 𝜉− − 𝜒− 𝜉+ ⟩ = (𝑎 − 𝑏)
√2 2
2
1
⟨0,0|𝑎𝑆𝑧 + 𝑏𝐼𝑧 |0,0⟩ = ( ) ⟨𝜒+ 𝜉− − 𝜒− 𝜉+ |𝑎𝑆𝑧 + 𝑏𝐼𝑧 |𝜒+ 𝜉− − 𝜒− 𝜉+ ⟩ = 0
√2
Thus the magnetic field introduces mixing between |1,0⟩ state and the |0,0⟩ state. We must
therefore diagonalize the submatrix
𝐴 𝑎−𝑏 𝐴 𝐴 𝑎−𝑏
− 0
( 4 2 )=( 4 )+( 2 2 )
𝑎−𝑏 3𝐴 𝐴 𝑎−𝑏 𝐴
− 0 − −
2 4 4 2 2
The second submatrix commutes with the first one. Its eigenvalues are easily determined
𝐴2 (𝑎−𝑏)2
to be ±√ 4 + so that the overall eigenvalues are
4
𝐴 𝐴2 (𝑎 − 𝑏)2
− ±√ +
4 4 4
Thus the spectrum consists of the following states:
𝐴 𝑎+𝑏
𝐹 = 1, 𝐹𝑧 = 1 𝐸= +
4 2
𝐴 𝑎+𝑏
𝐹 = 1, 𝐹𝑧 = −1 𝐸= −
4 2
𝐴 𝐴2 (𝑎 − 𝑏)2
𝐹 = 1,0; 𝐹𝑧 = 0 𝐸=− ±√ +
4 4 4
We can now put in numbers.
For 𝐵 = 10−4 T, the values in units of 10−6 eV are 1.451, 1.439, 0(10−10 ), -2.89.
For 𝐵 = 1 T, the values in units of 10−6 eV are 57.21, -54.32, 54.29 and 7 × 10−6 .
3. According to Eq. (12-17, Gaziorowicz) the energies of hydrogen-like states, including
relativistic + spin-orbit contributions is given by
1 𝑚𝑒 𝑐 2 (𝑍𝛼 )2 1 1 1 1 3
𝐸𝑛,𝑗 = − − 𝑚𝑒 𝑐 2 (𝑍𝛼 )4 3 ( − )
2 (1 + 𝑚𝑒 ) 𝑛 2 2 𝑛 𝑗 + 1 4𝑛
𝑀𝑝 2
The wavelength in a transition between two states is given by
2𝜋ℏ𝑐
𝜆=
Δ𝐸
where Δ𝐸 is the change in energy in the transition. We now considering the transitions 𝑛 =
3 1 1 1
3, 𝑗 = 2 → 𝑛 = 1, 𝑗 = 2 and 𝑛 = 3, 𝑗 = 2 → 𝑛 = 1, 𝑗 = 2. The corresponding energy
differences (neglecting the reduce mass effect) is
3 1 1 1 1 1 1
(3, → 1, ) 𝑚𝑒 𝑐 2 (𝑍𝛼 )2 (1 − ) + 𝑚𝑒 𝑐 2 (𝑍𝛼 )4 (1 − )
2 2 2 9 2 4 27
1 1 1 1 1 1 3
(3, → 1, ) 𝑚𝑒 𝑐 2 (𝑍𝛼 )2 (1 − ) + 𝑚𝑒 𝑐 2 (𝑍𝛼 )4 (1 − )
2 2 2 9 2 4 27
We can write these in the form
3 1 13
(3, → 1, ) Δ𝐸0 (1 + (𝑍𝛼 )2 )
2 2 48
1 1 1
(3, → 1, ) Δ𝐸0 (1 + (𝑍𝛼 )2 )
2 2 18
where
1 8
Δ𝐸0 = 𝑚𝑒 𝑐 2 (𝑍𝛼)2
2 9
The corresponding wavelengths are
3 1 13
(3, → 1, ) 𝜆0 (1 − (𝑍𝛼 )2 ) = 588.995 × 10−9 m
2 2 48
1 1 1
(3, → 1, ) 𝜆0 (1 − (𝑍𝛼 )2 ) = 589.592 × 10−9 m
2 2 18
We may use the two equations to calculate 𝜆0 and 𝑍. Dividing one equation by the other
we ger, after a little arithmetic 𝑍 = 11.5, which fits with the 𝑍 = 11 for sodium. (Note that
2𝜋ℏ𝑐 9𝜋ℏ
if we take for 𝜆0 the average of the two wavelengths, then, using 𝜆0 = = , we
Δ𝐸0 2𝑚𝑐(𝑍𝛼)2
get a seemingly unreasonably small value of 𝑍 = 0.4! This is not surprising. The ionization
potential for sodium is 5.1 eV instead of 𝑍 2 (13.6 eV), for reasons that will be discussed in
Chapter 14.)
4. (a) With 𝐽 = 1 and 𝑆 = 1, the possible values of the orbital angular momentum, such that
𝑗 = 𝐿 + 𝑆, 𝐿 + 𝑆 − 1, … , |𝐿 − 𝑆| can only be 𝐿 = 0,1,2. Thus the possible states are
𝑆13 , 𝑃13 , 𝐷13 . The parity of the deuteron is (−1)𝐿 asuming that the intrinsic parities of the
proton and neutron are taken to be +1. Thus the 𝑆 and 𝐷 states have positive parity and the
𝑃 state has opposite parity. Given parity conservation, the only possible admixture can be
the 𝐷13 state.
(b) The interaction with a magnetic field consist of three contributions: the interaction of
the spins of the proton and neutron with the magnetic field, and the 𝐋 ⋅ 𝐁 term, if 𝐿 is not
zero. We write
𝐻 = −𝐌𝐩 ⋅ 𝐁 − 𝐌𝐧 ⋅ 𝐁 − 𝐌𝐋 ⋅ 𝐁
where
𝑒𝑔𝑝 𝑒ℏ 𝐒𝐩
𝐌𝐩 = 𝐒𝐩 = (5.5792) ( )
2𝑀 2𝑀 ℏ
𝑒𝑔𝑛 𝑒ℏ 𝐒𝐧
𝐌𝐩 = 𝐒𝐧 = (−3.8206) ( )
2𝑀 2𝑀 ℏ
𝑒
𝐌𝐩 = 𝑳
2𝑀𝑟𝑒𝑑
We take the neutron and proton masses equal (= 𝑀) and the reduced mass of the two-
particle system for equal masses is 𝑀/2. For the 𝑆13 state, the last term does not contribute.
If we choose 𝐁 to define the 𝑧 axis, then the energy shift is
𝑒𝐵ℏ 3 𝑆𝑝𝑧 𝑆𝑛𝑧
− ⟨𝑆1 |𝑔𝑝 ( ) + 𝑔𝑛 ( )| 𝑆13 ⟩
2𝑀 ℏ ℏ
We write
𝑆𝑝𝑧 𝑆𝑛𝑧 𝑔𝑝 + 𝑔𝑛 𝑆𝑝𝑧 + 𝑆𝑛𝑧 𝑔𝑝 − 𝑔𝑛 𝑆𝑝𝑧 − 𝑆𝑛𝑧
𝑔𝑝 ( ) + 𝑔𝑛 ( ) = +
ℏ ℏ 2 ℏ 2 ℏ
It is easy to check that the last term has zero matrix elements in the triplet states, so that we
1 𝑆
are left with 2 (𝑔𝑝 + 𝑔𝑛 ) ℏ𝑧 , where 𝑆𝑧 is the 𝑧-component of the total spin. Hence
3 𝐵ℏ 𝑔𝑝 + 𝑔𝑛
⟨𝑆13 |𝐻1 |𝑆13 ⟩ = − 𝑚𝑠
2𝑀 2
where 𝑚𝑠 is the magnetic quantum number (𝑚𝑠 = 1,0, −1) for the total spin. We may
therefore write the magnetic moment of the deuteron as
𝑒 𝑔𝑝 + 𝑔𝑛 𝑒
𝜇𝑒𝑓𝑓 = − 𝐒 = −(0.8793) 𝐒
2𝑀 2 2𝑀
The experimental measurements correspond to 𝑔𝑑 = 0.8574 which suggests a small
admixture of the 𝐷13 to the deuteron wave function.