Content

Bohr’s atom and fine structure of the hydrogen atom 3

Angular momentum and spherical harmonics 3
The Stern-Gerlach experiment and discovery of the spin 6
The qubit model of the spin 11
Addition of angular momenta 13
Central problem and Bohr’s atom 15
Bohr’s hydrogen atom as a harmonic oscillator problem 19
Time-independent Perturbation theory 23
The spin-orbit coupling and fine structure of hydrogen 25
The hyperfine structure (21 cm cosmology) 30
Stark effect and Lamb shift 33
The Zeeman effect 36
The interaction between Bohr’s atom and radiation and quantum jumps 39
Time-dependent perturbation theory 39
Fermi’s Golden rule 41
Harmonic perturbations and detailed balance 42
Stimulated emission (LASER) and absorption by electromagnetic radiation 44
Spontaneous emission and blackbody radiation 49
Exact solution for two-level systems (MASER and NMR) 51
Two-level systems: Quantum computation 54
Angular momentum and spherical harmonics
I In quantum mechanics the angular momentum ~ r ×~
L=~ p is given by the operators
L̂1 = x̂2 p̂3 − x̂3 p̂2 , L̂2 = x̂3 p̂1 − x̂1 p̂3 , L̂3 = x̂1 p̂2 − x̂2 p̂1 . (1)
I By using the fundamental commutation relations [x̂i , p̂j ] = i~δij we compute the commutation relations

[L̂1 , L̂2 ] = i~L̂3 , [L̂3 , L̂1 ] = i~L̂2 , [L̂2 , L̂3 ] = i~L̂1 . (2)

I The square of the total angular momentum L̂2 = L̂2 + L̂2 + L̂2 commutes with the components L̂i , viz
1 2 3
2 2 2 2 2
L̂ = L̂1 + L̂2 + L̂3 , [L̂ , L̂i ] = 0. (3)

I Thus, we can diagonalize L̂2 and one of the components of the angular momentum operator. We consider
2
L̂3 |f i = µ|f i , L̂ |f i = λ|f i. (4)

We must always have µ2 ≤ λ.

I Next, we define the raising and lowering operators by

L̂± = L̂1 ± i L̂2 . (5)

Thus, L̂± |f i is an eigenvector of L̂3 with eigenvalue µ ± ~.

I In other words, starting from |f i we obtain via the application of L̂+ the eigenvectors with eigenvalues
µ + n~ where n is a positive integer. We must always have (µ + n~)2 ≤ λ and hence there is a maximum
value of n.
I The corresponding eigenvector is the highest weight state denoted by |fh i = |lli with corresponding
eigenvalue denoted by +~l.
I This highest weight state must also satisfy L̂+ |lli = 0 and L̂2 |lli = ~2 l(l + 1)|lli. Thus, λ = ~2 l(l + 1).
We have then
2 2
L̂3 |lli = ~l|lli , L̂+ |lli = 0 , L̂ |lli = ~ l(l + 1)|lli. (6)
I In the same manner we can show that there exists a lowest weight state |l − li with eigenvalue equals
−~l and which satisfies L̂− |l − li = 0. We have then
2 2
L̂3 |l − li = −~l|l − li , L̂− |l − li = 0 , L̂ |l − li = ~ l(l + 1)|l − li. (7)
Angular momentum and spherical harmonics
I In general, the eigenvalues of L̂3 will be denoted by ~m where m takes the values between −l and +l in N
integer steps. Thus, l = −l + N or equivalently l = N/2. In other words, there are 2l + 1 states in total
and l can be either integer (corresponding to ordinary angular momentum) or half-integer (corresponding
to spin). The eigenvectors will be denoted by |lmi such that
2 2
L̂ |lmi = ~ l(l + 1)|lmi , L3 |lmi = ~m|lmi
1 3
l = 0, , 1, , ... , m = −l, −l + 1, ..., l − 1, l. (8)
2 2
I In spherical coordinates the components of the angular momentum operator and the square of the total
angular momentum are given by

~ ∂ ∂
~ ∂ ∂
~ ∂
L̂1 = − sin φ − cot θ cos φ , L̂2 = cos φ − cot θ sin φ , L̂3 = . (9)
i ∂θ ∂φ i ∂θ ∂φ i ∂φ

1 ∂ ∂ 1 ∂2
 
2 2
L̂ = −~ (sin θ )+ . (10)
sin θ ∂θ ∂θ sin2 θ ∂φ2

I The common eigenfunctions of L̂2 and L̂3 are Y m (θ, φ) = hθ|hφ|lmi. They satisfy
l

1 ∂ ∂ 1 ∂2 ~ ∂
 
2 m 2 m m m
−~ (sin θ )+ Yl = ~ l(l + 1)Yl , Yl = ~mYl . (11)
sin θ ∂θ ∂θ 2
sin θ ∂φ 2 i ∂φ
I The explicit solution can be obtained by separation of variables. We write Y m (θ, φ) = Θm (θ) exp(imφ)
l l
where m is an integer, viz m = 0, ±1, ±2, ....
I We obtain the differential equation (with x = cos θ)

d dΘm m2
 
2 l m
(1 − x ) + [l(l + 1) − ]Θl = 0. (12)
dx dx 1− x2
This is the Legendre equation.
Angular momentum and spherical harmonics
I The solution is given in terms of the associated Legendre polynomial P m (x) by the equation
l
|m|  d |m|
m m m 2 2
Θl (θ) = APl (x) , Pl (x) = (1 − x ) Pl (x). (13)
dx
I Hence, the associated Legendre polynomial P m (x) is given in terms of the Legendre polynomial Pl (x)
l
which in turn is given by the so-called Rodrigues formula
1 d l 2
 
l
Pl (x) = (x − 1) . (14)
l
2 l! dx
From this equation it is clear that l is a positive integer and Pl (x) is a polynomial of degree l in x = cos θ.
Hence, if |m| > l then Plm (x) = 0 and the allowed values of l and m are thus given by
l = 0, 1, 2, ... , m = −l, −l + 1, ..., 0, ...., l − 1, l. (15)
As before we have 2l + 1 states for every value of l. However, l is here always an integer.
I The complete solution is therefore given by
m m imφ
Yl (θ, φ) = APl (cos θ)e . (16)
I We will impose the normalization condition
Z 2π Z π
m 2
sin θdθdφ |Yl (θ, φ)| = 1. (17)
0 0

We find
s
2l + 1 (l − |m|)!
A= . (18)
4π (l + |m|)!

m
 = (−1) , m ≥ 0 ,  = 1 , m ≤ 0. (19)

We can also check the orthonormalization condition

Z 2π Z π
m ∗ s
sin θdθdφ [Yl (θ, φ)] Yt (θ, φ) = δlt δms . (20)
0 0
The Stern-Gerlach experiment and discovery of the spin
I The Stern-Gerlach experiment is one of the greatest experiments in physics, atomic physics and quantum
mechanics.
I This experiment plays also a major role in the foundation and philosophy of quantum mechanics. The
Stern-Gerlach apparatus can be used to prepare the initial state of the system, i.e. it allows us to select
any desired polarization for the initial state.
I More importantly, the Stern-Gerlach experiment provides an almost idealized conceptual model for the
process of quantum measurement as we will discuss below.
I It was designed originally to decide between Larmor’s classical theory and Sommerfeld’s old quantum
theory describing the motion of charged particles in magnetic fields. As it turns out, both theories are in
fact wrong and the correct description is given by quantum mechanics.
I More precisely, this experiment was designed to test the so-called ”space quantization”, i.e. the
quantization of the angular momentum suggested originally by Bohr.
I It led immediately to the discovery of the ”spin” which is a purely quantum property of the electron.
I In the Bohr-Sommerfeld model we imagine the atom as a positively charged dense nucleus with negatively
charged electrons moving in orbits around the center.
I In order for the electrons to not spiral towards the center, as they radiate energy in the electric field of the
nucleus, Bohr restricted their motion to specific orbits, called orbitals, determined by some integer (the
principal quantum number n). This is called orbital quantization and it allowed Bohr to explain why atoms
emit and absorb radiation only under a discrete form, i.e. at a discrete set of electromagnetic frequencies.
In fact, Bohr was also successful in deriving the celebrated Rydberg formula for these frequencies.
I Bohr’s model relied on the fundamental assumption that the angular moment of the electron must be
quantized. We write this in the form
I
pϕ dϕ = nϕ h.

Thus, in the ground state of the atom the electron must have only two values of the angular momentum
along any direction in space corresponding to nϕ = ±1.
I This prediction was called space quantization and Stern devised his experiment to test it directly. In fact,
Stern was very sceptical about this prediction and he went in his scepticism as far as to raise a wager to
quite physics if Bohr’s quantization turns out to be correct. Stern was shortly joined by Gerlach who was
instrumental in the success of the experiment. Yet, it is Stern who won the Nobel prize in physics on this
work (called the molecular ray method) in 1943.
I As we will see this one assumption, which seemed to enrage Stern, turns out to be wrong yet the beams of
atoms prepared in the ground states (such as the silver and the hydrogen atoms used in the experiments)
are observed to suffer a splitting into two streams in a non-uniform magnetic field as predicted by Bohr
(but for the wrong reason).
The Stern-Gerlach experiment and discovery of the spin
I The orbital angular momentum is indeed quantized but not according to the above rule and the
Stern-Gerlach experiment which sought to discover this space quantization ended up discovering the spin
quantum number and vindicating the new theory of quantum mechanics.
I We can also add to the above quantization of the angular momentum, following Sommerfeld, the following
radial quantization
I
pr dr = nr h.

I This will extend Bohr’s original circular orbits to elliptical orbits. These quantization conditions govern the
so-called Bohr’s correspondence principle which states that in the limit of large quantum numbers nϕ and
nr the predictions of the old quantum theory should reduce to those of classical physics.
I In the Stern-Gerlach experiment (1922) a beam of hot silver atoms (characterized by a single unpaired
electron) is sent through a non-uniform magnetic field. After going through the magnets the beam reaches
a detector plate. The atoms, as we will see, are characterized by a dipole magnetic moment and thus as
they move in the non-uniform magnetic field they will experience a torque which acts differently on the two
ends of the dipoles leading to a net force on the atoms. This causes the atoms to deflect differently, in the
non-uniform magnetic field, according to the magnitude of their magnetic moments.
I This experiment was repeated with hydrogen atoms (which are characterized by a single electron) by
Phipps and Taylor in 1927.
I Both silver and hydrogen are neutral atoms found in the ground state l = 0 (as opposed to the assumption
of the Bohr-Sommerfeld old quantum mechanics which predicts l = 1).
I Yet, in both cases the Stern-Gerlach experiment shows that the beam of atoms splits in fact into two
beams, as originally thought by Bohr and Sommerfeld but not for the right reasons, signaling therefore the
existence of another quantum property.
I This quantum property is the so-called spin angular momentum with value s = 1/2 which was first
proposed by two graduate students (Goudsmit and Uhlenbeck) and then confirmed later by Dirac in his
quantum relativistic theory of the electron.
I In the case of the hydrogen atom the extra spin angular momentum is associated with its single electron
whereas in the case of the silver atom the extra spin quantum number is associated with its unpaired
outermost electron.
I Thus, the Stern-Gerlach experiment invalidates both classical mechanics and the old quantum theory. The
Stern-Gerlach experiment is a major vindication of the new quantum theory of Heisenberg, Schrodinger,
Dirac, Pauli and Bohr.
The Stern-Gerlach experiment and discovery of the spin
I In general if a beam of atoms with total angular momentum J~ = ~ L+S~ is prepared in the orbital ground
state l = 0 then allowed to go through the Stern-Gerlach appartus it will be observed to split into 2s + 1
beams corresponding to the eigenvalues ms of the spin angular momentum Sz which are given by
ms = s, s − 1, ..., −s. In other words, if we measure the angle between the spin angular momentum and
the z−axis there can only be 2s + 1 possible values.
I Every atom acts as an electromagnet, i.e. it is characterized by a magnetic dipole moment µ ~ . Thus, it will
experience a torque µ~ ×B ~ in a magnetic field B
~ which makes the dipole moment µ ~ want to align with the
~ giving therefore a minimum energy. The corresponding potential energy is
direction of the magnetic field B
given by

H = −~ ~
µ.B.
I In the simplest case of the hydrogen atom we have a single electron moving around its orbit and thus
creating a tiny loop of electric current I . The magnetic moment of this current is µl = I .A where A is the
area of the loop. If v is the speed of the electron and r is the radius of the orbit then 2πr is the distance
traveled by the electron in a single period, i.e. v /2πr is the inverse period and ev /2πr is precisely the
current, viz I = ev /2πr where e is the charge of the electron. The angular momentum of the electron is
L = mrv . From all these considerations we have
e e
µl = L⇒µ
~l = − ~
L.
2m 2m
We also note that the magnetic moment and the angular momentum are in opposite directions because of
the negative charge of the electron.
I Similarly, the magnetic dipole moment of a spinning charge is given in terms of its spin angular momentum
~ by the equation (with q = −e)
S
gq gq
µ
~s = ~⇒H =−
S ~ B.
S. ~
2m 2m
The factor g is the gyromagnetic ratio which is given by g = 2 for the electron.
I In a non-uniform magnetic field there exists, in addition to the above torque, a force on the magnetic
dipole given by

~ = ∇(~
F ~
~ µ.B).
The Stern-Gerlach experiment and discovery of the spin
I Let us imagine that the beam is directed in the direction of the y -axis and that the non-uniform magnetic
field is given by

~ = −αx iˆ + (B0 + αz)k̂ , ∇

B ~B~ = 0.
I The parameter α provides the non-uniformity. B0 represents a uniform magnetic field giving rise to the
so-called Larmor precession. This effect is given by the following expectation values of the spin angular
momentum components

~ ~ ~
hSx i = sin α cos γB0 t , hSy i = − cos α sin γB0 t , hSz i = cos α.
2 2 2
~ precesses around the z-axis at a constant angle α with a frequency ω = B0 t (Larmor
I Thus, hSi
frequency). The above result is an instance of Ehrenfest’s theorem, viz

d
~ = h~
hSi ~
µ × Bi.
dt
I We return to the non-uniform magnetic field and we compute the corresponding force. We find the result

~ = γα(−Sx iˆ + Sz k̂).
F
I But we know from Larmor precession that Sx oscillates rapidly and averages to zero leaving only the
z-component of the force, viz

~ = γαSz k̂.
F
I For a spin 1/2 particle the beam is either deflected up for the eigenvalue m = +~/2 of Sz or down for the
eigenvalue m = −~/2.
I This splitting into two beams was observed by Gerlach for the first time in February 1922.
I The correct explanation of the Stern-Gerlach experiment is thus not in terms of Bohr-Sommerfeld old
quantum theory which suggested that the ground state of the silver atom is characterized by a quantized
angular momentum equal l = 1.
I This is because we know that this ground state is in fact characterized by l = 0 and thus does not lead to
any splitting (and even if it was characterized by l = 1 it would have given a splitting into three beames
corresponding to l = +1, 0, −1 and not two beams corresponding to l = +1, −1).
The Stern-Gerlach experiment and discovery of the spin
I The correct explanation is given in terms of the spin angular momentum of the outermost unpaired
electron. The total angular momentum J~ = ~ L+S ~ with l = 0 and s = 1/2 leads to j = 1/2 and thus a
splitting into two beams.
I In general the beam is split into 2s + 1 components corresponding to the 2s + 1 values of the force
associated themselves with the 2s + 1 values of the spin, viz
~ = γα~mk̂ , m = s, s − 1, ..., −s.
F
I This is the basic physics behind the Stern-Gerlach experiment.
I Thus, the Stern-Gerlach experiment is an experimental proof for the spin quantum number and not for
space quantization (although we also know today that orbital angular momentum is indeed quantized).
I More importantly, Stern-Gerlach experiment is an experimental proof for the new theory of quantum
mechanics.

Stern-Gerlach experiment. Source: https://physicsworld.com/

Discovery of the spin. Source: https://plato.stanford.edu/

The qubit model of the spin
I In summary, the Stern-Gerlach experiment comes with two main results:
I ) First: The magnetic dipole moment of the atoms is quantized not continuous (discrete set of angles
instead of a continuous distribution).
II ) Second: In the ground state of atoms we have zero orbital angular momentum l = 0 which corresponds to
zero magnetic dipole moment µ = 0 giving rise therefore to no deflection at all. Yet, we observe two peaks.
I Conclusion: There must exist a new physical quantity making an extra contribution to the magnetic dipole
moment (spin). This contribution has no relation with the rotational motion of the electron.
I The spin can be characterized by a single bit or more precisely by a single quantum bit or qubit as follows.
1) The output of the Stern-Georlach apparatus consists of two beams | + Z i (up) and | − Z i (down). We
call this the z−Stern-Gerlach apparatus (since it measures the spin or the qubit in the ẑ-direction as it is
oriented in the ẑ-direction).
2) We place now an x-Stern-Gerlach apparatus oriented in the x̂-direction (and thus measures the spin or
qubit in the x̂-direction) in series with the original ẑ-Stern-Gerlach apparatus.
3) Let us block the beam |Z −i. Thus, all transmitted atoms have magnetic dipole moment which is up. And
classically since the magnetic dipole moment is oriented in the ẑ-direction there will be no deflection in a
magnetic field oriented in the x̂-direction. In other words, one should have one central peak. However,
again we observe two peaks labeled | + X i, | − X i.
4) Let us again block the beam | − X i and place a third z-Stern-Gerlach apparatus in the way of the beam
| + X i. We expect to see one peak corresponding to the fact that the atoms in the beam | + X i retained
their | + Z i orientation. But again we observe a splitting into two beams | + Z i and | − Z i.
5) The conclusion is that the state | + Z i contains equal amounts of | + X i and | − X i and the state
| + X i contains equal amounts of | + Z i and | − Z i.
I In terms of the qubit computational states |0i and |1i we have then the following correspondence :

| + Z i ≡ |0i , | − Z i ≡ 1i.

1 1
| + X i ≡ |+i = √ (|0i + |1i) , | − X i ≡ |−i √ (|0i − |1i).
2 2
I Thus, the z-Stern-Gerlach apparatus measures the spin quantum number or the qubit in the computational
basis {|0i, |1i}. Similarly, the x-Stern-Gerlach apparatus measures the spin quantum number or the qubit
in the computational basis {|+i, |−i}.
I The spin can thus be completely captured by the qubit model.
The qubit model of the spin

Source: Nielsen and Chuang

Addition of angular momenta
~ in addition to the orbital angular momentum ~
I In the presence of a non-zero spin angular momentum S, L,
the total angular momentum J~ becomes given by

J~ = ~ ~
L + S. (21)

I We have two sets of compatible operators: {~ L2 , L3 , S

~2 , S3 } and {~
L2 , S
~2 , J~2 , J3 }.
I The eigenvectors |lsjj3 i of J~2 , J3 , ~
L2 and S
~2 can be given as linear combinations of the eigenvectors
|lmi|sσi of ~ L2 , L3 , S
~2 and S3 with coefficients C lmsσ known as the Clebsch-Gordan coefficients.
jj3
I Explicitly, we have

~2 2
L |lmi|sσi = ~ l(l + 1)|lmi|sσi , L3 |lmi|sσi = ~m|lmi|sσi
~2 |lmi|sσi = ~2 s(s + 1)|lmi|sσi , S3 |lmi|sσi = ~σ|lmi|sσi.
S (22)

~2 2 ~2 |lsjj3 i = ~s(s + 1)|lsjj3 i

L |lsjj3 i = ~ l(l + 1)|lsjj3 i , S
2 2
J~ |lsjj3 i = ~ j(j + 1)|lsjj3 i , J3 |lsjj3 i = ~j3 |lsjj3 i. (23)
I For spin s = 1/2 we have explicitly

lj3 − 1 1 1 1 11 lj3 + 1 1 − 1 1 1 1
|lsjj3 i = Cjj 2 2 2 |lj3 − i| i + Cjj 2 2 2 |lj3 + i| − i
3 2 22 3 2 2 2
1 1
= A|lj3 − i|+i + B|lj3 + i|−i. (24)
2 2
I By using the condition J~2 = ~
L2 + S
~2 + 2L3 S3 + L+ S− + L− S+ we can compute the two constraints
s
1 1 1 1 1
 
2 2 2
J~ |lj3 − i|+i = ~ l(l + 1) + j3 + |lj3 − i|+i + ~ l(l + 1) − j32 + |lj3 + i|−i. (25)
2 4 2 4 2

s
1 1 1 1 1
 
2 2 2
J~ |lj3 + i|−i = ~ l(l + 1) − j3 + |lj3 + i|−i + ~ l(l + 1) − j32 + |lj3 − i|+i. (26)
2 4 2 4 2
Addition of angular momenta

I Using now the condition J~2 |lsjj3 i = ~2 j(j + 1)|lsjj3 i and comparing with the above two constraints leads
to two equations in the unknowns A and B which are equivalent. The first equation reads

s
1 1
 
A l(l + 1) + j3 + +B l(l + 1) − j32 + = j(j + 1)A. (27)
4 4

I We must also have |A|2 + |B|2 = 1. Explicitly, we get the solution

 r r

l+ 1 +j l+ 1 −j3


2 3 2
, j = l + 1/2


 2l+1 2l+1
(A, B) = r r . (28)
l+ 1 −j l+ 1 +j3

3


 2 , − 2 j = l − 1/2
2l+1 2l+1

