Chapter 1

Module IV: Quantum

Properties of Electrons

1.1 Electron angular momentum

1. Electrons in free space can carry quantized orbital angular momentum when pro-
jected in specific direction.

2. The behaviour of particle waves can be viewed as analogously to the waves trav-
elling on a string.

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3. Electron moving in nth circular orbit of radius rn , the total distance is equal to

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circumference of the orbit 2πrn . Hence, the equation can be written as
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2πrn = n.λ (1.1)
B
4. We know that De-broglie wavelength is given as

h h
λ= = (1.2)
p mvn

Substituting for λ in above equation, we have

h
2πrn = n. (1.3)
mvn

5. The above equation can be rewritten as

h
n. = m.vn .rn = r × p (1.4)
2π

6. This equation (de Broglie hypothesis) successfully proves Bohr’s second postulate
stating the quantization of angular momentum of the orbiting electron. We can
also conclude that the quantized electron orbits and energy states are due to the
wave nature of the electron.

1
2 CHAPTER 1. MODULE IV: QUANTUM PROPERTIES OF ELECTRONS

7. Consider a quantum system with defined angular momentum ~j revolving around

the orbit. First length of the angular momentum is quantized and take discrete
values with no other values other than mentioned below:.
p 1 3
} j (j + 1) for j = 0, , 1, , 2, ... (1.5)
2 2

Figure 1.1: Angular momentum

8. Hence the end ~

p point of the angular momentum j lies on the surface of the sphere
of radius } j (j + 1). The projection on an axis in space is quantized and can
take values m = −j, −j + 1, ...j − 1, j.

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9. The discrete quantum number ’m’ is integral or half integral, depending on whether

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j is integral or half integral.
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1.1.1 Angular momentum

Angular momentum is very important quantity to understand the behaviour of

a particle under central potential. Example is hydrogen atom where electron
is attacted toward the proton by inverse square Coulomb attraction. Angular
momentum is vector operator comprising of three defined commutation relation.
The angular momentum of a particle about a given point is defined as

L = ~r × P~ (1.6)

where r is the position vector and ’p’ is the momentum of the particle. Writing
the equation in different co-ordinate form as

Lx = y.Pz − z.Py
Ly = z.Px − x.Pz
Lz = x.Py − y.Px

Angular momentum resulting from any kind of motion in space comes under orbital
angular momentum.
1.1. ELECTRON ANGULAR MOMENTUM 3

1.1.2 angular momentum operator

The operators Px , Py , Pz represents the component of linear momentum annd operate
on the wave function. Here
∂
Px = −i} (1.7)
∂x
∂
Py = −i} (1.8)
∂y
∂
Pz = −i} (1.9)
∂z
Angular momentum operators Lx , Ly , Lz obey the following commutation relation:

[Lx , Ly ] = i}Lz (1.10)

[Ly , Lz ] = i}Lx (1.11)
[Lz , Lx ] = i}Ly (1.12)

1. Lx , Ly , Lz do not commute with each other.

2. If the particle has a wave function which is an eigen function of Lx , then it will
not be an eigne function of Ly /Lz .

3. it is possible to have Lx = Ly = Lz = 0 .

4. If Lx is known for a given state, then you cannot know Ly and Lz .

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In addition to this,

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L+ = Lx + i.Ly (1.13)

B L− = Lx − i.Ly

L+ and L− are rising and lowering operators. Square of the angular momentum is an
(1.14)

important measurable quantity (Hermitian operator) and can be written as

L2 = L2x + L2y + L2z (1.15)

The operator L2 with any of the component operator Lx , Ly or Lz is

 2  2
Lx , Lz + L2y , Lz + L2z , Lz
     
L , Lz = (1.16)
 2 
L , Lz = 0 (1.17)
 2 
L , Lx = 0 (1.18)
 2 
L , Ly = 0 (1.19)

Eigen values of L2 are spherical harmonic function with polar co-ordinates , the operator
can be
1 ∂2
 
2 2 1 ∂ ∂
L = −} sin θ + (1.20)
sin θ ∂θ ∂θ sin2 θ ∂φ2
and the above equation is known as Legendre equation.
4 CHAPTER 1. MODULE IV: QUANTUM PROPERTIES OF ELECTRONS

1.1.3 Space quantization

The
 2 commutation
 relation for the angular momentum are given as [Lx , Ly ] = i}Lz ,
L , Lz = 0 with cyclic permutations. The allowed values of quantized angular mo-
mentum
p J lies on the surface of the sphere of radius and can be written as J =
} j (j + 1). The projection on an axis in space is quantized and can take values
m = −j, −j + 1, ...j − 1, j. Customarily, the z-component is singled out with other two
components retaining indefinate or fluctuating values. Definite magnitude and direction
of one component of angular momentum is known as space quantization, with spin
involved, m and j can also take half-integer values.

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Figure 1.2: Space Quantization

B p
Using J = } j (j + 1), one can find qunatum mechanical allowed values of angular
momentum in the units of } as
p
1. for j=0, J = j (j + 1) = 0 unit
p √
2. for j=1, J = 1 (1 + 1) = 2 unit
p √
3. for j=2, J = 2 (2 + 1) = 6 unit
p √
4. for j=3, J = 3 (3 + 1) = 12 unit

1.2 Electron Spin and Spin Angular Momentum

.
In previous section, the square of the angular momementum r x p of a particle have values
j (j + 1) }2 with j for any non-negative value. If we do not use the r x p expression, then
system may take any non-negative integer or half integer value. Most of the systems at
the atomic level angular momementum corresponding to half-integral quantum number
2
not integral quantum number. if an electron having angular momentum with value 3}4 ,
it cannot be due to motion but other intrinisc property called spin.
1.2. ELECTRON SPIN AND SPIN ANGULAR MOMENTUM 5

Spin angular momentum has a fixed value, generally denoted by ’S’ and eigen value of
S 2 can be written as
S 2 = s (s + 1) }2 (1.21)
2 2
For s = 12 , the value of S 2 = 3}4 , which is fixed value. However, for z-axis, you get ± }2 .
This is true in all cases where electron is travelling from electron gun towards screen
or photoelectric effect. The spin angular momentum is therefore intrinsic or built-in
angular momentum. Examples for spin half particles are proton’s and neutrons which
has s= 12 .
Z-component of spin angular momentum of a particle is a physically measurable quantity
and hence there must be Hermitian operator corresponding to it.
S2 = Sx2 + Sy2 + Sz2 (1.22)
Sz = ms } for ms = ..... (1.23)
[Sx , Sy ] = i}Sz (1.24)
[Sy , Sz ] = i}Sx (1.25)
[Sz , Sx ] = i}Sy (1.26)
S+ = Sx + i.Sy (1.27)
S− = Sx − i.Sy (1.28)

1.2.1 Larmor’s Theorem

For a static magnetic moment or a classical current loop, this torque tends to line up
the magnetic moment with the magnetic field B, so this represents its lowest energy

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configuration. But if the magnetic moment arises from the motion of an electron in

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orbit around a nucleus, the magnetic moment is proportional to the angular momentum

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of the electron. The torque exerted then produces a change in angular momentum which
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is perpendicular to that angular momentum, causing the magnetic moment to precess
around the direction of the magnetic field rather than settle down in the direction of
B
the magnetic field. This is called Larmor precession.
Larmor precession is the precession of the magnetic moment of an object about an
external magnetic field. Objects with a magnetic moment also have angular momentum
and effective internal electric current proportional to their angular momentum. The
external magnetic field exerts a torque on the magnetic moment:
~ = γ J~ × B
~ ×B
τ =µ ~ (1.29)
where τ is the torque, µ is the magnetic

dipole moment, J is the angular momentum
eg
vector, γ gyromagnetic ratio = − 2m and B is the external magnetic field. Angular
momentum vector J~ precesses about the external field axis with an angular frequency
known as the Larmor frequency:
ω = −γ × B (1.30)
where ω is the agnular frequency.Larmor frequency is independent of the angle between
J and B which does affect how much J changes during the precession cycle.
When a torque is exerted perpendicular to the angular momentum J, it produces a
change in angular momentum 4J, which is perpendicular to L, causing it to precess
about the z-axis. Labelling the precession angle, as ω:
4L L sin θ4φ e
τ= = = LB sin θ (1.31)
4t 4t 2me
6 CHAPTER 1. MODULE IV: QUANTUM PROPERTIES OF ELECTRONS

he precession angular velocity (Larmor frequency) is

dφ e
ωlarmor = = B (1.32)
dt 2m
These relationships for a finite current loop extend to the magnetic dipoles of electron
orbits and to the intrinsic magnetic moment associated with electron spin. There is also
a characteristic Larmor frequency for nuclear spins.
In the case of the electron spin precession, the angular frequency associated with the
spin transition is usually written in the general form:
eg
ω= B (1.33)
2me

1.2.2 Spin Magnetic Moment

The basic source for producing a magnetic field is a current loop. A charged particle
particle going in a circle with large velocities is equivalent to a current loop. Such a
motion corresponds to a magnetic moment and angular momentum.
Consider a particle of mass (M), with a charge (q) moving in a circle of radius (r) with
a constant speed (v). Time (T) period of the motion is given by
2πr
T = (1.34)
v
v
Here, the particle crosses through any point on the circle 2πr times per unit time and
qv
accordingly the total charge of goes through any point on the circule per unit time.
Hence current is given as
2πr

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qv
I= (1.35)

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magnetic moment due to this motion is

B µ = Iπr2 =
q
2M
(M vr) (1.36)

here, ’Mvr’ is the angular momentum of the particle. Both the magnetic moment and
angular momentum are in the same direction, we can rewrite the above equation as
q
µz = Iπr2 = (Iz ) (1.37)
2M
For an electron (q=-e) with mass (M=me ), we can
e
µz = πr2 = − (Iz ) (1.38)
2me
if the particle is in eigen state of Lz , then Iz is definite and equal to eigne value of m}.
Then the above equation is written as
 
e}
µz = − (me ) (1.39)
2me
The equation in bracket is known as Bohr magneton with symbol µB and regarded
as basic unit in magnetism.  
e}
µB = − (1.40)
2me
1.3. STERN-GERLACH EXPERIMENT 7

1.3 Stern-Gerlach Experiment

The Stern–Gerlach experiment demonstrated that the spatial orientation of angular mo-
mentum is quantized. The silver atoms were sent through a spatially varying magnetic
field, which deflected them before they struck a detector screen, such as a glass slide.
Particles with non-zero magnetic moment are deflected, due to the magnetic field gra-
dient, from a straight path. The screen reveals discrete points of accumulation, rather
than a continuous distribution,owing to their quantized spin.

Figure 1.3: Stern-Gerlach-Experiment

The Stern–Gerlach experiment involves sending a beam of silver atoms through an

inhomogeneous magnetic field and observing their deflection. The results show that
particles possess an intrinsic angular momentum that is closely analogous to the angu-
lar momentum of a classically spinning object, but that takes only certain quantized

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values. Another important result is that only one component of a particle’s spin can

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be measured at one time, meaning that the measurement of the spin along the z-axis

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destroys information about a particle’s spin along the x and y axis. The experiment is
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normally conducted using electrically neutral particles such as silver atoms. This avoids

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the large deflection in the path of a charged particle moving through a magnetic field
B
and allows spin-dependent effects to dominate.
If the particle is treated as a classical spinning magnetic dipole, it will precess in a
magnetic field because of the torque that the magnetic field exerts on the dipole (see
torque-induced precession). If it moves through a homogeneous magnetic field, the forces
exerted on opposite ends of the dipole cancel each other out and the trajectory of the
particle is unaffected. However, if the magnetic field is inhomogeneous then the force
on one end of the dipole will be slightly greater than the opposing force on the other
end, so that there is a net force which deflects the particle’s trajectory. If the particles
were classical spinning objects, one would expect the distribution of their spin angular
momentum vectors to be random and continuous. Each particle would be deflected by
an amount proportional to the dot product of its magnetic moment with the external
field gradient, producing some density distribution on the detector screen. Instead, the
particles passing through the Stern–Gerlach apparatus are deflected either up or down
by a specific amount. This was a measurement of the quantum observable now known
as spin angular momentum, which demonstrated possible outcomes of a measurement
where the observable has a discrete set of values or point spectrum.
Although some discrete quantum phenomena, such as atomic spectra, were observed
much earlier, the Stern–Gerlach experiment allowed scientists to directly observe sep-
aration between discrete quantum states for the first time in the history of science.
Theoretically, quantum angular momentum of any kind has a discrete spectrum, which
is sometimes briefly expressed as "angular momentum is quantized".
1.5. STARK EFFECT 9

1.5 Stark Effect

The Stark effect is the shifting and splitting of spectral lines of atoms and molecules
due to the presence of an external electric field. It is the electric-field analogue of the
Zeeman effect, where a spectral line is split into several components due to the presence
of the magnetic field.The splitting of atomic spectral lines as a result of an externally
applied electric field is called the Stark effect. As the splitting of a line of the helium
spectrum shows, the splitting is not symmetric like that of the Zeeman effect.
The splitting of the energy levels by an electric field first requires that the field polarizes
the atom and then interacts with the resulting electric dipole moment. That dipole
moment depends upon the magnitude of Mj, but not its sign, so that the energy levels
show splitting proportional to quantum numbers J+1 or J+1/2, for integer and half-
integer spins respectively.

Figure 1.5: Experimental set up and Stark Energy Splitting

The Stark effect is responsible for the pressure broadening (Stark broadening) of spectral
lines by charged particles in plasmas. For most spectral lines, the Stark effect is either
linear (proportional to the applied electric field) or quadratic with a high accuracy. The
Stark effect can be observed both for emission and absorption lines. The Stark effect

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has been of marginal benefit in the analysis of atomic spectra, but has been a major

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tool for molecular rotational spectra.

-
Starting with hydrogen atom,
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p2 e2
Ho = − (1.45)

B 2m
and adding electric term to above equation resulting
r

H 1 = e.E.~x (1.46)

The selection rules on the matrix elemetns are ~x are

< n0 , l0 , m0 | ~xn, l, m >6= 0, l0 = l ± 1, m0 = m (1.47)

if n=1, then l=0, therefore no first stark effect.

if n=2, then we have two l values, then l=0,1 which means the line may appear between
0 and 1. The listing states can be Ψ200 , Ψ211 , Ψ211 , Ψ211̄ .

1.6 Gyromagnetic Ratio (qualitative)

Any free systems with a constant gyromagnetic ratio (γ), such as rigid system of charges,
a nucleus or an electron, when placed in an external magnetic field (B) that is not aligned
with its magnetic moment, will precess at a frequency that is proportional to the external
field
γ
f= B (1.48)
2π
10 CHAPTER 1. MODULE IV: QUANTUM PROPERTIES OF ELECTRONS

Gyromagnetic ratio for an isolated electron is given by

−e −ge µB
γe = ge = (1.49)
2me }

for γ = 1.760859770 × 1011 S −1 T −1 and ge = 2.002319.

Gyromagnetic ratio for an isolated neutrons is given by
e gµN
γe = g= (1.50)
2mp }

1.7 Bohr Magneton (qualitative)

Bohr magneton with symbol µB and regarded as basic unit in magnetism.
 
e}
µB = −
2me

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