Atomic and Molecular Physics

Instructor-
Golam Dastegir Al-Quaderi
Associate Professor
Department of Physics, DU

1
 Wave Mechanics
• Double-Slit Experiments with Particles:
• The definitive evidence for the wave nature of light
was deduced from the double-slit experiment
performed by Thomas Young in 1801.
• In principle, it should be possible to do double-slit
experiments with particles and thereby directly
observe their wavelike behaviour.
• However, the technological difficulties of producing
double slits for particles are formidable.
• Such experiments did not become possible until long
after the time of de Broglie.
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 Wave Mechanics
• Double-Slit Experiment with Electrons:
• The first double-slit experiment with electrons
was done in 1961.
• A diagram of the apparatus is shown in the figure:
• Electrons from the
filament 𝐹𝐹 are
accelerated
through 50 kV and
pass through the
double slit.
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 Wave Mechanics
• The de Broglie wavelength of such electrons is
𝜆𝜆 = 5.4 pm= 5.4 × 10−12 m.
• The double slit has of separation 2.0 𝜇𝜇m and
width 0.5 𝜇𝜇m.
• A photograph of the resulting intensity pattern is
as follows:

• .

Intensity pattern of double-slit experiment with electrons. 4

 Wave Mechanics
• The intensity pattern produced by the
electrons can be found by a similar treatment
as in optics.

5
 Wave Mechanics
• Double-Slit Experiment with Neutrons:
• A similar experiment can be done for neutrons.
• A beam of neutrons from a nuclear reactor is
slowed to a room-temperature “thermal” energy
distribution (average 𝐾𝐾 ≈ 𝑘𝑘𝑘𝑘 ≈ 0.025 eV).
• A specific wavelength can be selected by a
scattering process similar to Bragg diffraction.

• .

6
 Wave Mechanics
• Neutrons of kinetic energy of 0.00024 eV and de
Broglie wavelength 1.85 nm are passed through a
gap of diameter 148 𝜇𝜇m (104+22+22=148).
• In the center of the gap was a boron wire (highly
absorptive for neutrons) of diameter 104 𝜇𝜇m.
• The neutrons could pass on either side of the
wire through slits each of width 22 𝜇𝜇m.
• The intensity of neutrons that pass through this
double slit was observed by sliding across the
beam another slit having a detector behind it.
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 Wave Mechanics
• The wavelength can be deduced from the slit
separation (𝑑𝑑 = 104 + 11 + 11 𝜇𝜇m = 126 𝜇𝜇m)
and fringe spacing (Δ𝑦𝑦 = 75 𝜇𝜇m):
𝑑𝑑Δ𝑦𝑦
𝜆𝜆 = = 1.89 nm
𝐷𝐷 𝟕𝟕𝟕𝟕 𝝁𝝁m
• This result agrees very
well with the de Broglie
wavelength of 1.85 nm
selected for the neutron
beam.
The spacing between the maxima is about 75μm
Source:R. Gahler and A. Zeilinger, American Journal of Physics 59, 316 (1991). 8
 Wave Mechanics
• Through Which Slit Does the Particle Pass?
• We could want to determine through which slit a particle
(such as an electron) would pass in a double-slit
experiment.
• We could surround each slit with an electromagnetic loop
that causes a meter to deflect whenever a charged particle
or perhaps a particle with a magnetic moment passes
through the loop.

• .

9
 Wave Mechanics
• In such an experiment, the result would no longer
be an interference pattern on the screen.
• Instead we would observe the net or resultant of
two patterns with “hits” in front of each slit.
• No matter what sort of device we use to
determine through which slit the particle passes,
the interference pattern will be destroyed.
A classical particle must pass through one slit or
the other; only a wave can reveal interference,
which depends on parts of the wavefront passing
through both slits and then recombining.
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 Wave Mechanics
• Principle of Complementarity: In a double-slit
experiment with particles:
• A. When we ask through which slit the particle passed,
we are investigating only the particle aspects of its
behavior, and we cannot observe its wave nature (the
interference pattern).
• The process of detecting the particle has necessarily
scattered it and this scattering destroys the
interference pattern.
• B. Conversely, when we study the wave nature, we
cannot simultaneously observe the particle nature.

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 Wave Mechanics
The particle will behave as a particle or a wave, but we
cannot observe both aspects of its behavior
simultaneously.
• This curious aspect of quantum mechanics is called the
principle of complementarity.
• It states that a complete description of a photon or a
material particle, such as an electron, cannot be made,
in terms of only particle properties or only wave
properties, but that both aspects of its behavior must
be considered.
• However, the particle and wave natures cannot be
observed simultaneously.

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 Wave Mechanics
• Foundations of Wave Mechanics: The two-slit
experiment with light (photon) or electron
demonstrates the fundamental rules on which
the quantum mechanical description is built.
• To get the rules we consider three cases:
• Case-1: Detection of Particle at a Slit: If we
determine the particle, its probability of
occurrence becomes 1 at a particular position
near one slit.
• That makes the particle pass along a trajectory
through only one slit.
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 Wave Mechanics
• Hence this particular particle does not have a
chance to move through the other hole/slit.
• Hence, NO interference patter occurs.
• The resultant pattern
on the screen is the
addition of individual
“single-slit diffraction
patterns” of the electrons
passing through each slit:
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 Wave Mechanics
• Case-2: No Detection of Particle Near a Slit: On
the other hand, (i.e. we do not detect the
particle), the particle has probability of passing
through any one of the two slits.
• Hence, the “probability wave” (i.e. the de Broglie
wave) passes through both the slits and interfere
(producing a fringe on the screen).

• .

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 Wave Mechanics
• Case2A: Low Intensity Beam: To make the idea of
probability wave passing through both slits even
stronger, we can perform a double-slit experiment with
extremely low intensity of particle beam.
• If we use such a low intensity that only one particle
pass through a slit at any time (particles are few and far
between) we can still observe an intensity pattern.

• .

The buildup of an electron interference pattern with very low intensity of electron beam.
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 Wave Mechanics
• In such an experiment (case 2A):
Individual electrons eventually produce the
characteristic interference fringes.
• This indeed shows that each single electron has a
certain probability of being at a certain position
in the double-slit experiment.
• Hence, we can conjecture:
The probability of finding a particle at any point
depends on the amplitude of its de Broglie wave at
that point.

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 Wave Mechanics
• Spreading of Wave After Detection: Suppose
we detect the particle at any slit.
• After the detection of the particle, at a slit, its
position is not further detected up to the
screen.
• This makes the particle’s probability wave
spread out again and create a “single-slit
diffraction pattern” on the screen.

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 Wave Mechanics
• An experiment involving two slits opening up
separately will produce two single slit
diffraction patterns to be recorded separately.

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 Wave Mechanics
• Rules of Wave Mechanics:
• A. Complex Nature of the Wave Function: The de
Broglie wave in general would be a complex function of
position and time:
𝜓𝜓 𝑟𝑟⃗, 𝑡𝑡 ~ 𝐴𝐴 exp 𝑖𝑖 𝑘𝑘. 𝑟𝑟⃗ − 𝜔𝜔𝜔𝜔
𝜓𝜓 𝑥𝑥, 𝑡𝑡 ~ 𝜓𝜓 𝑥𝑥, 𝑡𝑡 exp 𝑖𝑖(𝑘𝑘𝑘𝑘 − 𝜔𝜔𝜔𝜔)
• This is because, there is no requirement that the de
Broglie wave must be real.
• The general form of the wave function will be:
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐹𝐹(𝑘𝑘𝑘𝑘 − 𝜔𝜔𝜔𝜔)
for propagation in the forward direction.

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 Wave Mechanics
• B. Calculation of Probability Density: The
probability must be non-negative number
between 0 and 1.
• Taking the argument of a function makes it
periodic in space or time, which is not always
true.
• Taking the amplitude as the probability
density makes it non-negative.

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 Wave Mechanics
• However, in analogy with classical physics, in which the
intensity of any wave is proportional to the square of
its amplitude, we have
probability density of observing a particle
∝ | de Broglie wave amplitude |2
𝑃𝑃 ∝ 𝐴𝐴 2
• Recall that the amplitude of the de Broglie wave is not
the same everywhere and hence also not the
probability.
• Normalization of the wave function makes the
probability lie between 0 and 1.

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 Wave Mechanics
• C. Addition of Probability Amplitudes:
• If an event can occur in more than one way (e.g. a
particle having two slits that it could pass
through), then there is an amplitude (and a wave)
for each path/outcome involved in the event.
• The total wave function would be the sum of the
individual wave functions for the outcomes:
Ψ = 𝜓𝜓1 + 𝜓𝜓2 + ⋯ + 𝜓𝜓𝑛𝑛
• Total probability is:
𝑃𝑃 ∝ Ψ 2

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 Wave Mechanics
• To further solidify the above idea, consider a
variant of the double slit experiment.
• What happens if one slit is covered during the
experiment?
• In this case one obtains a symmetric curve
peaked around the center of the open slit,
much like the pattern formed by bullets shot
through a hole in armor plate.

24
 Wave Mechanics
• The probability of passing through one slit is
found from the square of the individual wave
functions:
𝜓𝜓1 2
and 𝜓𝜓2 2
• The total result
of counts will be
simply the sum
of two results.

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 Wave Mechanics
• The interference pattern will be lost.
• The accumulated result is simply the sum of
the individual results : 𝜓𝜓1 2 + 𝜓𝜓2 2

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 Wave Mechanics
• In contrast to this, now, consider both slits
open.
• Then, clearly we observe interference pattern
even for one electron passing at a time.

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 Wave Mechanics
• Hence, we say that the electron is in a superposition
state given by the linear combination of each state:
Ψ = 𝜓𝜓1 + 𝜓𝜓2
• Thus, the probability of detecting the electron at the
screen is equal to the quantity:
𝜓𝜓1 + 𝜓𝜓2 2
and not to 𝜓𝜓1 2 + 𝜓𝜓2 2 .
• Hence, we find,
𝑃𝑃 ∝ Ψ 2 = 𝜓𝜓1 + 𝜓𝜓2 2
= 𝜓𝜓1 2 + 𝜓𝜓2 2 + 2 𝜓𝜓1 𝜓𝜓2 cos 𝛿𝛿
where 𝛿𝛿 is the phase difference between the waves.
Note that the interference term is: 2 𝜓𝜓1 𝜓𝜓2 cos 𝛿𝛿
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 Wave Mechanics
• Born Interpretation: The statistical (probabilistic)
interpretation of the wave function is due to Max
Born.
• In one-dimensional case we have:
The probability that a particle will be found in the
infinitesimal interval 𝒅𝒅𝒅𝒅 about the point 𝒙𝒙, at time
𝒕𝒕, denoted by 𝝆𝝆(𝒙𝒙, 𝒕𝒕) 𝒅𝒅𝒅𝒅, is
𝑑𝑑𝑑𝑑 𝑥𝑥, 𝑡𝑡 = 𝜌𝜌 𝑥𝑥, 𝑡𝑡 𝑑𝑑𝑑𝑑 = 𝜓𝜓 𝑥𝑥, 𝑡𝑡 2 𝑑𝑑𝑑𝑑
• 𝜌𝜌 𝑥𝑥, 𝑡𝑡 = 𝑑𝑑𝑑𝑑/𝑑𝑑𝑑𝑑 is called the probability density.
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 Wave Mechanics
• Properties of 𝜓𝜓 𝑥𝑥, 𝑡𝑡 :
• A. Continuity: Because of its relation to probabilities,
we insist that 𝜓𝜓 𝑥𝑥, 𝑡𝑡 be a single-valued and continuous
function of 𝑥𝑥 and 𝑡𝑡 so that no ambiguities can arise
concerning the predictions of the theory.
• B. Smoothness: Furthermore, the wave function
𝜓𝜓 𝑥𝑥, 𝑡𝑡 must be a smooth function.
• C. Normalization: Because the particle must be
somewhere along the x-axis, the probabilities summed
over all values of 𝑥𝑥 must add to 1:
∞
� 𝜓𝜓 𝑥𝑥, 𝑡𝑡 2 𝑑𝑑𝑑𝑑 =1
−∞

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 Wave Mechanics
• Example-1: Normalizing the Wave function
• The initial (at 𝑡𝑡 = 0 ) wave function of a
particle is given as 𝜓𝜓 𝑥𝑥, 0 = 𝐶𝐶 exp(−|𝑥𝑥|/
𝑥𝑥0 ), where 𝐶𝐶 and 𝑥𝑥0 are constants.
• Sketch this function. Find 𝐶𝐶 in terms of 𝑥𝑥0
such that 𝜓𝜓 𝑥𝑥, 0 is normalized.
• Solution-1: The given wave function is
symmetric, decaying exponentially from the
origin in either direction.
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 Wave Mechanics
• Solution-1 (contd.): The decay length 𝑥𝑥0
represents the distance over which the wave
amplitude is diminished by the factor 1/𝑒𝑒
from its maximum value 𝜓𝜓 0,0 = 𝐶𝐶.

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 Wave Mechanics
• Solution-1 (contd.): The requirement of
normalization is:
∞ ∞
2
1=� 𝜓𝜓 𝑥𝑥, 0 𝑑𝑑𝑑𝑑 = 𝐶𝐶 2 � exp −2|𝑥𝑥|/𝑥𝑥0 𝑑𝑑𝑑𝑑
−∞ −∞
• The integrand is an even function. Hence we
have,
∞ 2
2
2𝐶𝐶 𝑥𝑥0
1 = 2𝐶𝐶 � exp −2𝑥𝑥/𝑥𝑥0 𝑑𝑑𝑑𝑑 = = 𝐶𝐶 2 𝑥𝑥0
0 2
• Hence, 𝐶𝐶 = 1/ 𝑥𝑥0 is the normalization constant.

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 Wave Mechanics
• Example-2: Calculate the probability that the
particle will be found within the interval
− 𝑥𝑥0 ≤ 𝑥𝑥 ≤ 𝑥𝑥0 for the wave function
𝜓𝜓 𝑥𝑥, 0 = 𝐶𝐶 exp(−|𝑥𝑥|/𝑥𝑥0 )
where 𝐶𝐶 = 1/ 𝑥𝑥0 .
• Solution-2: The probability is the area under
the curve of probability density, i.e.
𝑑𝑑𝑑𝑑 𝑥𝑥 /𝑑𝑑𝑑𝑑 = 𝜓𝜓 𝑥𝑥, 0 2 from −𝑥𝑥0 to 𝑥𝑥0 .

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 Wave Mechanics
• Solution-2 (contd.): Integrating the probability density
over the specified interval, we get
𝑥𝑥0 𝑥𝑥0
𝑑𝑑𝑑𝑑
𝑃𝑃 −𝑥𝑥0 ≤ 𝑥𝑥 ≤ 𝑥𝑥0 = � 𝑑𝑑𝑑𝑑 = � 𝜓𝜓 𝑥𝑥, 0 2 𝑑𝑑𝑑𝑑
−𝑥𝑥0 𝑑𝑑𝑑𝑑 −𝑥𝑥0
𝑥𝑥0 𝑥𝑥0
⇒ 𝑃𝑃′ = 2 � 𝜓𝜓 𝑥𝑥, 0 2
𝑑𝑑𝑑𝑑 = 2𝐶𝐶 2 � exp −2𝑥𝑥/𝑥𝑥0 𝑑𝑑𝑑𝑑
0 0
′
𝑥𝑥0
2
⇒ 𝑃𝑃 = 2𝐶𝐶 1 − 𝑒𝑒 −2 = 0.8647
2
• Hence, the chance of the particle to be detected within
this range is about 87%.

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 Wave Mechanics
• Wave function for a Free Particle:
• A free particle is the one subject to no force.
• This implies that the particle can move without
any external influence.
• From classical mechanics, we expect that the
momentum of a free particle should be
conserved.
• That implies we have a particular momentum of
the de Broglie wave that is also conserved.

36
 Wave Mechanics
• Hence the momentum uncertainty is zero as its
momentum has a single value.
• Furthermore, since its position is in no way
constrained, its position uncertainty is as large as
can be.
• The wave number of the de Broglie wave of a free
particle is:
𝑘𝑘 = 2𝜋𝜋/𝜆𝜆 = 𝑝𝑝/ℏ
• Frequency of the de Broglie wave is:
𝜔𝜔 = 𝐸𝐸/ℏ

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 Wave Mechanics
• The wave function should have a definite values of 𝑘𝑘
and 𝜔𝜔 :
𝜓𝜓𝑘𝑘 𝑥𝑥, 𝑡𝑡 = 𝐴𝐴 exp 𝑖𝑖𝑖𝑖𝑖𝑖 − 𝑖𝑖𝑖𝑖𝑖𝑖 = 𝐴𝐴𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘−𝜔𝜔𝜔𝜔)
• Because the variables 𝑥𝑥 and 𝑡𝑡 occur only in the
combination (𝑘𝑘𝑘𝑘 − 𝜔𝜔𝜔𝜔), the oscillation is a forward
traveling wave.
• Similarly, we may have backward moving component
wave as:
𝐵𝐵𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘+𝜔𝜔𝜔𝜔)
• Furthermore, it is a plane wave having a plane wave-
front.

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 Wave Mechanics
• Probability Distribution:
• The probability density is uniform given by:
𝜌𝜌 𝑥𝑥, 𝑡𝑡 = 𝑑𝑑𝑑𝑑/𝑑𝑑𝑑𝑑 = 𝜓𝜓𝑘𝑘 2 = 𝐴𝐴2
• That is, the probability of finding this particle
in any interval of the 𝑥𝑥-axis is the same as that
for any other interval of equal length.
• The probability also does not change with
time.

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 Wave Mechanics
• Energy of a Non-Relativistic Free Particle:
• For a free particle, the total energy
𝐸𝐸 = 𝑝𝑝𝑝𝑝 2 + 𝑚𝑚2 𝑐𝑐 4
• In the non-relativistic case, we have 𝑣𝑣 ≪ 𝑐𝑐 and hence,
2 2 1/2 2 4 1/2
𝑝𝑝
𝑐𝑐 𝛾𝛾 2
𝑚𝑚 𝑣𝑣
𝐸𝐸 = 𝑚𝑚𝑐𝑐 2 1+ 2 4 = 𝑚𝑚𝑐𝑐 2 1+
𝑚𝑚 𝑐𝑐 𝑚𝑚2 𝑐𝑐 2
1 2 2
• But 𝛾𝛾 = 1 − 𝑣𝑣 2 /𝑐𝑐 2 ≈1− 𝑣𝑣 /𝑐𝑐 ≈1
2
1
𝑣𝑣 2 2 1 𝑣𝑣 2 1
⇒ 𝐸𝐸 ≈ 𝑚𝑚𝑐𝑐 2 1 + ≈ 𝑚𝑚𝑐𝑐 2 1+ = 𝑚𝑚𝑐𝑐 2
+ 𝑚𝑚𝑣𝑣 2
𝑐𝑐 2 2 𝑐𝑐 2 2

40
 Wave Mechanics
• Hence, for a non-relativistic particle, the total
2 𝑝𝑝2
energy is: 𝐸𝐸 = 𝑚𝑚𝑐𝑐 +
2𝑚𝑚
• Since, for the non-relativistic case, 𝑝𝑝2 /2𝑚𝑚 =
𝑚𝑚𝑣𝑣 2 /2 ≪ 𝑚𝑚𝑐𝑐 2 , rest mass energy acts as a mere
constant.
• The particle does not have enough energy to
excite a pair creation.
• Hence, the rest mass energy can be conveniently
taken as the reference of energy measurement.

41
 Wave Mechanics
• Hence, for a non-relativistic particle, taking the zero of the
energy as the rest-mass energy, we get the total energy as:
𝑝𝑝2 ℏ2 𝑘𝑘 2
𝐸𝐸 = =
2𝑚𝑚 2𝑚𝑚
• Dispersion Relation: For nonrelativistic particles 𝜔𝜔 is
related to 𝑘𝑘 as:
𝑝𝑝2 ℏ2 𝑘𝑘 2
𝐸𝐸 = = 𝜔𝜔𝜔 =
2𝑚𝑚 2𝑚𝑚
• Hence, the dispersion relation is:
ℏ𝑘𝑘 2
𝜔𝜔 𝑘𝑘 =
2𝑚𝑚

42
 Wave Mechanics
• Wave Function of Initially Detected Free Particle: We
may establish (by measurement) that our particle is
initially within some range Δ𝑥𝑥 (about 𝑥𝑥0 ).
• In this case we would have obtained a wave packet of
the form:
∞
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = � 𝑎𝑎 𝑘𝑘 exp 𝑖𝑖𝑖𝑖𝑖𝑖 − 𝑖𝑖𝑖𝑖 𝑘𝑘 𝑡𝑡 𝑑𝑑𝑑𝑑
−∞
• The position uncertainty will disperse over time, after
the detection of the particle, as the wavepacket will
spread.

43
 Wave Mechanics
• Each of the plane wave constituents moves
with a different velocity 𝑣𝑣𝑝𝑝 = 𝜔𝜔/𝑘𝑘 (the phase
velocity).
• The group velocity of the packet is:
𝑣𝑣𝑔𝑔 = 𝑑𝑑𝑑𝑑/𝑑𝑑𝑑𝑑

44
 Wave Mechanics
• Example-3: (a) Find the wave function 𝜓𝜓(𝑥𝑥, 0) that results
from taking the function
𝑎𝑎 𝑘𝑘 = 𝐶𝐶𝐶𝐶/ 𝜋𝜋 exp −𝛼𝛼 2 𝑘𝑘 2
where 𝐶𝐶 and 𝛼𝛼 are constants.
• (b) Estimate the product Δ𝑥𝑥Δ𝑘𝑘 for this case.
• Solution-3: The wave function 𝜓𝜓(𝑥𝑥, 0) is given by the
Fourier integral:
∞
𝜓𝜓 𝑥𝑥, 0 = � 𝑎𝑎 𝑘𝑘 exp 𝑖𝑖𝑖𝑖𝑖𝑖 𝑑𝑑𝑑𝑑
−∞
𝑘𝑘=∞
𝐶𝐶𝐶𝐶
𝜓𝜓 𝑥𝑥, 0 = � exp −𝛼𝛼 2 𝑘𝑘 2 exp 𝑖𝑖𝑖𝑖𝑖𝑖 𝑑𝑑𝑑𝑑
𝑘𝑘=−∞ 𝜋𝜋

45
 Wave Mechanics
• Solution-3 (contd.): Thus, to evaluate the integral,
we complete the square:
2 2
𝑖𝑖𝑖𝑖 𝑥𝑥
𝑖𝑖𝑖𝑖𝑖𝑖 − 𝛼𝛼 2 𝑘𝑘 2 = − 𝛼𝛼𝛼𝛼 − − 2
2𝛼𝛼 4𝛼𝛼
• The second term on the right is constant for the
integration over 𝑘𝑘;
• To integrate the first term, we change the
variable with the substitution, 𝑧𝑧 = 𝛼𝛼𝛼𝛼 − 𝑖𝑖𝑖𝑖/2𝛼𝛼
𝑧𝑧=∞
𝐶𝐶𝐶𝐶 𝑥𝑥 2 2
𝑑𝑑𝑑𝑑
𝜓𝜓 𝑥𝑥, 0 = exp − 2 � exp −𝑧𝑧
𝜋𝜋 4𝛼𝛼 𝑧𝑧=−∞ 𝛼𝛼
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 Wave Mechanics
∞
• Solution-3 (contd.): But,∫−∞ exp −𝑧𝑧 2 𝑑𝑑𝑑𝑑 = 𝜋𝜋, giving:
𝑥𝑥 2 𝑥𝑥 2
𝜓𝜓 𝑥𝑥, 0 = 𝐶𝐶 exp − 2 = 𝐶𝐶 exp −
4𝛼𝛼 2𝛼𝛼
• This function 𝜓𝜓 𝑥𝑥, 0 above is a Gaussian function.
• (b) We can define the “width” Δ𝑥𝑥 of the Gaussian
function as 𝛼𝛼:
Δ𝑥𝑥 = 𝛼𝛼
• This is because, if 𝛼𝛼 large, so also the spread in the
Gaussian function.

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 Wave Mechanics
• Solution-3 (contd.): The wave function in the 𝑘𝑘-space is
the Fourier integral of 𝜓𝜓 𝑥𝑥, 0 i.e. 𝑎𝑎(𝑘𝑘):
𝐶𝐶𝐶𝐶
𝑎𝑎 𝑘𝑘 = exp −𝛼𝛼 2 𝑘𝑘 2
𝜋𝜋
• Comparing this with the position space wave function
𝜓𝜓 𝑥𝑥, 0 = 𝐶𝐶 exp −𝑥𝑥 2 /4𝛼𝛼 2 , whose width is Δ𝑥𝑥 = 𝛼𝛼,
we get
exp −𝛼𝛼 2 𝑘𝑘 2 = exp −𝑘𝑘 2 /4 Δ𝑘𝑘 2
⇒ −𝛼𝛼 2 𝑘𝑘 2 = −𝑘𝑘 2 / 4 Δ𝑘𝑘 2 ⇒ Δ𝑘𝑘 = 1/2𝛼𝛼
• Thus the uncertainty product is Δ𝑥𝑥Δ𝑘𝑘 = 1/2 (constant)

48
 Wave Mechanics
• Differential Equation for Wave Function of a
Free Particle: For a free particle, the wave
function has a single wave length 𝜆𝜆 = ℎ/𝑝𝑝.
• Now consider the quantity:
𝑝𝑝̂ 𝜓𝜓(𝑥𝑥, 𝑡𝑡)
• We can consider this as the momentum operator
acting on the wave function giving the
“eigenvalue” equal to the momentum 𝑝𝑝 = ℏ𝑘𝑘:
𝑝𝑝̂ 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑝𝑝𝑝𝑝 𝑥𝑥, 𝑡𝑡 = ℏ𝑘𝑘𝑘𝑘(𝑥𝑥, 𝑡𝑡)
49
 Wave Mechanics
• Plugging in the free-particle wave function, we should
get:
𝑝𝑝̂ 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑝𝑝̂ 𝐶𝐶 exp 𝑖𝑖(𝑘𝑘𝑘𝑘 − 𝜔𝜔𝜔𝜔) = ℏ𝑘𝑘𝑘𝑘(𝑥𝑥, 𝑡𝑡)
• This can be achieved if we assume an operator form of
the momentum:
𝜕𝜕
𝑝𝑝̂ ≡ −𝑖𝑖𝑖
𝜕𝜕𝜕𝜕
𝜕𝜕 𝑖𝑖𝑖𝑖𝑖𝑖−𝑖𝑖𝑖𝑖𝑖𝑖
⇒ 𝑝𝑝̂ 𝐶𝐶 exp 𝑖𝑖𝑖𝑖𝑖𝑖 − 𝑖𝑖𝑖𝑖𝑖𝑖 = −𝑖𝑖𝑖𝑖𝑖 𝑒𝑒
𝜕𝜕𝜕𝜕
= −𝑖𝑖𝑖 𝑖𝑖𝑖𝑖𝑖𝑖𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖−𝑖𝑖𝑖𝑖𝑖𝑖
• For a free particle, there is no potential energy.
50
 Wave Mechanics
• The Wave Equation or The Schrödinger Equation: As a
postulate, we assume a wave equation for a particle as the
Schrödinger equation:
𝜕𝜕
� 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑖𝑖ℏ 𝜓𝜓(𝑥𝑥, 𝑡𝑡)
𝐻𝐻
𝜕𝜕𝜕𝜕
� is the energy (Hamiltonian) operator, and 𝑝𝑝� is
where 𝐻𝐻
the momentum operator.
• In terms of the position representation of the momentum
operator, the Schrödinger equation for a (free) particle is:
ℏ2 𝜕𝜕 2 𝜕𝜕
− 2
𝜓𝜓(𝑥𝑥, 𝑡𝑡) = 𝑖𝑖𝑖 𝜓𝜓(𝑥𝑥, 𝑡𝑡)
2𝑚𝑚 𝜕𝜕𝑥𝑥 𝜕𝜕𝜕𝜕

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 Wave Mechanics
• The Schrödinger equation states that:
The time evolution of the wave function is
governed by the Hamiltonian operator
• There is no PROOF or DERIVATION of
Schrödinger equation. It is just a postulate of
quantum mechanics.
Schrödinger’s equation cannot be derived from
other basic principles of physics; it is a basic
principle in itself.
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 Wave Mechanics
• The justification of Schrödinger equation lies
in its ability to get theoretical predictions that
have been experimentally verified numerous
times.
• Schrödinger’s equation has turned out to be
remarkably accurate in predicting the results
of experiments.
• It is a fundamental equation of physics just
like Newton’s second law of motion.

53
 Wave Mechanics
• Heuristic/Plausibility Argument in favour of
Schrödinger equation:
• Recall that, Schrödinger equation is valid in
the non-relativistic case only.
• For a free particle, the wave function is:
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐴𝐴 exp 𝑖𝑖𝑖𝑖𝑖𝑖 − 𝑖𝑖𝑖𝑖𝑖𝑖
• Taking derivative twice, we get:
𝜕𝜕 2 2 (𝑖𝑖𝑖𝑖𝑖𝑖−𝑖𝑖𝑖𝑖𝑖𝑖) 2
2
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐴𝐴 𝑖𝑖𝑖𝑖 𝑒𝑒 = −𝑘𝑘 𝜓𝜓(𝑥𝑥, 𝑡𝑡)
𝜕𝜕𝑥𝑥
54
 Wave Mechanics
• From the dispersion relation for the non-
relativistic free particle 𝐸𝐸 = 𝑝𝑝2 /(2𝑚𝑚) = 𝜔𝜔𝜔 =
ℏ2 𝑘𝑘 2 /(2𝑚𝑚), we get:
2
2𝑚𝑚
𝑘𝑘 = 2 𝐸𝐸
ℏ
• Hence,
𝜕𝜕 2 2
2𝑚𝑚
2
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = −𝑘𝑘 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = − 2 𝐸𝐸𝐸𝐸 𝑥𝑥, 𝑡𝑡
𝜕𝜕𝑥𝑥 ℏ
ℏ2 𝜕𝜕 2
⇒− 2
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐸𝐸𝜓𝜓 𝑥𝑥, 𝑡𝑡 = ℏ𝜔𝜔𝜔𝜔 𝑥𝑥, 𝑡𝑡
2𝑚𝑚 𝜕𝜕𝑥𝑥
55
 Wave Mechanics
• But we have for a free particle:
𝜕𝜕 𝜕𝜕 (𝑖𝑖𝑖𝑖𝑖𝑖−𝑖𝑖𝑖𝑖𝑖𝑖)
𝑖𝑖𝑖 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑖𝑖𝑖𝑖𝑖 𝑒𝑒 = −𝑖𝑖 2 ℏ𝜔𝜔𝜔𝜔(𝑥𝑥, 𝑡𝑡)
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕
𝜕𝜕
⇒ 𝑖𝑖𝑖 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = ℏ𝜔𝜔𝜔𝜔 𝑥𝑥, 𝑡𝑡 = 𝐸𝐸𝜓𝜓(𝑥𝑥, 𝑡𝑡)
𝜕𝜕𝜕𝜕
• This suggests that for a free particle the time
evolution is related to the energy of the particle.
• Now the “Hamiltonian” 𝐻𝐻 � is the energy operator
and the energy eigenvalue equation is:
� 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐸𝐸𝐸𝐸(𝑥𝑥, 𝑡𝑡)
𝐻𝐻

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 Wave Mechanics
• This gives the Schrödinger equation ,
𝜕𝜕𝜕𝜕 𝑥𝑥, 𝑡𝑡
� 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑖𝑖𝑖
𝐻𝐻
𝜕𝜕𝜕𝜕
• Hence by the heuristic argument, the Schrödinger
equation for a free particle is:
ℏ2 𝜕𝜕 2 𝜕𝜕
− 2
𝜓𝜓(𝑥𝑥, 𝑡𝑡) = 𝑖𝑖𝑖 𝜓𝜓(𝑥𝑥, 𝑡𝑡)
2𝑚𝑚 𝜕𝜕𝑥𝑥 𝜕𝜕𝜕𝜕
• It must be emphasized that the above is just a
plausibility argument and does not constitute a
derivation.

57
 Wave Mechanics
• Solution of the Free Particle Schrödinger Equation:
• Since for a free particle, there is no potential involved,
we can assume a stationary state solution of the form:
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑠𝑠 𝑥𝑥 𝑓𝑓(𝑡𝑡)
• This is a variable separable form, and plugging into the
Schrödinger equation for a free particle, we get:
ℏ2 𝑑𝑑2 𝑑𝑑
− 𝑓𝑓 𝑡𝑡 2
𝑠𝑠 𝑥𝑥 = 𝑖𝑖𝑖𝑖𝑖 𝑥𝑥 𝑓𝑓(𝑡𝑡)
2𝑚𝑚 𝑑𝑑𝑥𝑥 𝑑𝑑𝑑𝑑
• Rearranging (since 𝑠𝑠 𝑥𝑥 𝑓𝑓 𝑡𝑡 ≠ 0 in general):
ℏ2 1 𝑑𝑑2 𝑖𝑖𝑖 𝑑𝑑
− 2
𝑠𝑠 𝑥𝑥 = 𝑓𝑓(𝑡𝑡)
2𝑚𝑚 𝑠𝑠 𝑥𝑥 𝑑𝑑𝑥𝑥 𝑓𝑓 𝑡𝑡 𝑑𝑑𝑑𝑑
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 Wave Mechanics
• The left-hand side is a function of 𝑥𝑥 only, while the
right-hand side is a function of 𝑡𝑡 only. Hence, both
must be equal to a constant (i.e. constant function).
• We can take the constant depending on the physical
situation.
• We take,
ℏ2 1 𝑑𝑑2 𝑖𝑖𝑖 𝑑𝑑
− 2
𝑠𝑠 𝑥𝑥 = 𝑓𝑓 𝑡𝑡 = 𝜔𝜔𝜔
2𝑚𝑚 𝑠𝑠 𝑥𝑥 𝑑𝑑𝑥𝑥 𝑓𝑓 𝑡𝑡 𝑑𝑑𝑑𝑑
• Integrating second relation we get:
ln 𝑓𝑓(𝑡𝑡) = −𝑖𝑖𝑖𝑖𝑖𝑖 + 𝑐𝑐

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 Wave Mechanics
• Upon exponentiation: 𝑓𝑓 𝑡𝑡 = 𝑒𝑒 𝑐𝑐 𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖
• Again integrating the right-hand equation:
ℏ2 1 𝑑𝑑2 ℏ2 𝑘𝑘 2
− 2
𝑠𝑠 𝑥𝑥 = ℏ𝜔𝜔 =
2𝑚𝑚 𝑠𝑠 𝑥𝑥 𝑑𝑑𝑥𝑥 2𝑚𝑚
1 1 𝑑𝑑2
⇒− 2 2
𝑠𝑠 𝑥𝑥 = 1
𝑘𝑘 𝑠𝑠 𝑥𝑥 𝑑𝑑𝑥𝑥
𝑑𝑑2
⇒ 2 𝑠𝑠 𝑥𝑥 + 𝑘𝑘 2 𝑠𝑠 𝑥𝑥 = 0
𝑑𝑑𝑥𝑥
which has a solution : 𝑠𝑠 𝑥𝑥 = 𝐴𝐴 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖
• Hence the complete solution is: 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐴𝐴′ 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖−𝑖𝑖𝑖𝑖𝑖𝑖
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 Wave Mechanics
• Time Independent Form of Schrödinger Equation: For
a free particle, the Schrödinger equation is:
ℏ2 𝜕𝜕 2 𝜕𝜕
− 2
𝜓𝜓(𝑥𝑥, 𝑡𝑡) = 𝑖𝑖𝑖 𝜓𝜓(𝑥𝑥, 𝑡𝑡)
2𝑚𝑚 𝜕𝜕𝑥𝑥 𝜕𝜕𝜕𝜕
• Plugging in the solution (for a stationary state),
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐴𝐴 exp 𝑖𝑖𝑖𝑖𝑖𝑖 − 𝑖𝑖𝑖𝑖𝑖𝑖 , we get:
ℏ2 𝜕𝜕 2
− 2
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = ℏ𝜔𝜔𝜔𝜔 𝑥𝑥, 𝑡𝑡 = 𝐸𝐸𝐸𝐸(𝑥𝑥, 𝑡𝑡)
2𝑚𝑚 𝜕𝜕𝑥𝑥
• This is the time-independent form of the Schrödinger
equation for a free particle, which is basically the
energy eigenvalue equation: 𝐻𝐻 � 𝜓𝜓 = 𝐸𝐸𝐸𝐸
61
 Wave Mechanics
• Wave Function of a Particle in a Potential:
• Note that, the de Broglie postulate, 𝜆𝜆 = ℎ/𝑝𝑝, says the
wavelength 𝜆𝜆 of a particle’s wave function will change
if 𝑝𝑝 changes.
• But the momentum 𝑝𝑝 changes only under the
influence of a force 𝐹𝐹⃗ = −𝛻𝛻𝑈𝑈 due to some potential
energy 𝑈𝑈.
• Note that, conventionally we denote the potential
energy by 𝑉𝑉 = 𝑉𝑉(𝑟𝑟⃗, 𝑡𝑡) or in the conservative case
𝑉𝑉 = 𝑉𝑉(𝑟𝑟⃗).
• Furthermore, we call the potential energy as simply the
“potential”.

62
 Wave Mechanics
• Now, for a particle acted upon some force, i.e. in
the presence of a potential, the momentum 𝑝𝑝
and hence the wavelength 𝜆𝜆 will change with
time.
• But a wavelength is not even well defined if it
changes very rapidly.
A non-sinusoidal wave:

The separation between an

adjacent pair of maxima
differs from that between
• . the closest adjacent pair
of minima.

63
 Wave Mechanics
• Hence, for a particle acted upon some force,
functions which are more complicated than the
simple sinusoidal wave are required to describe
the wave function.
• For a particle acted upon some potential, the
total non-relativistic energy is:
𝑝𝑝2
𝐸𝐸 = + 𝑉𝑉(𝑥𝑥, 𝑡𝑡)
2𝑚𝑚
• We have seen that the momentum operator has
the position representation: 𝑝𝑝̂ ≡ −𝑖𝑖𝑖𝑖𝑖/𝜕𝜕𝜕𝜕
64
 Wave Mechanics
• While the Hamiltonian operator, which has the
eigenvalue equal to the energy 𝐸𝐸, governs the time
evolution of the wave function via the Schrödinger
� 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑖𝑖𝑖 𝜕𝜕𝜕𝜕(𝑥𝑥, 𝑡𝑡)/𝜕𝜕𝜕𝜕
equation : 𝐻𝐻
• Hence, in analogy with that of a free particle, the
Schrödinger equation for a particle in a potential
becomes:
ℏ2 𝜕𝜕 2 𝜕𝜕
− 2
+ 𝑉𝑉(𝑥𝑥, 𝑡𝑡) 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑖𝑖𝑖 𝜓𝜓 𝑥𝑥, 𝑡𝑡
2𝑚𝑚 𝜕𝜕𝑥𝑥 𝜕𝜕𝜕𝜕
• We can not PROVE this to be true but we can
POSTULATE it.

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 Wave Mechanics
• Time-Independent Schrödinger Equation for particle
in a Potential:
• In this case we get, 𝑉𝑉 𝑥𝑥, 𝑡𝑡 = 𝑉𝑉(𝑥𝑥) and the so called
time-independent Schrödinger equation:
ℏ2 𝜕𝜕 2
− 2
+ 𝑉𝑉(𝑥𝑥) 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐸𝐸𝐸𝐸(𝑥𝑥, 𝑡𝑡)
2𝑚𝑚 𝜕𝜕𝑥𝑥
• We can variable separate the solution
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑠𝑠 𝑥𝑥 𝑓𝑓 𝑡𝑡 = 𝜓𝜓 𝑥𝑥 𝜙𝜙 𝑡𝑡
ℏ2 𝜕𝜕 2
⇒ − 2
+ 𝑉𝑉 𝑥𝑥 𝜓𝜓 𝑥𝑥 = 𝐸𝐸𝜓𝜓(𝑥𝑥)
2𝑚𝑚 𝜕𝜕𝑥𝑥

66
 Wave Mechanics
• Together with the above, we have the time
equation:
𝜕𝜕
𝑖𝑖𝑖 𝜙𝜙 𝑡𝑡 = ℏ𝜔𝜔𝜔𝜔 𝑡𝑡 = 𝐸𝐸𝜙𝜙(𝑡𝑡)
𝜕𝜕𝜕𝜕
• In 3D the we have:
ℏ2 2 𝜕𝜕
− 𝛻𝛻 + 𝑉𝑉(𝑟𝑟⃗) 𝜓𝜓 𝑟𝑟⃗, 𝑡𝑡 = 𝑖𝑖𝑖 𝜓𝜓 𝑟𝑟⃗, 𝑡𝑡
2𝑚𝑚 𝜕𝜕𝜕𝜕
𝜓𝜓 𝑟𝑟⃗, 𝑡𝑡 = 𝜓𝜓 𝑟𝑟⃗ 𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖

67
 Wave Mechanics
• Applications of Schrödinger Equation:
• A. Solutions for Constant Potential Energy:
• For the special case of a constant potential energy,
equal to 𝑉𝑉 = 𝑈𝑈0 , we get:
ℏ2 𝑑𝑑2
− 2
𝜓𝜓 𝑥𝑥 + 𝑈𝑈0 𝜓𝜓 𝑥𝑥 = 𝐸𝐸𝐸𝐸(𝑥𝑥)
2𝑚𝑚 𝑑𝑑𝑥𝑥
• Assuming that 𝐸𝐸 > 𝑈𝑈0 , we get:
𝑑𝑑2 𝜓𝜓 2 𝜓𝜓(𝑥𝑥)
= −𝑘𝑘
𝑑𝑑𝑥𝑥 2
where 𝑘𝑘 = 2𝑚𝑚 𝐸𝐸 − 𝑈𝑈0 /ℏ2

68
 Wave Mechanics
• The most general solution to the equation is:
𝜓𝜓 𝑥𝑥 = 𝐴𝐴 sin(𝑘𝑘𝑘𝑘) + 𝐵𝐵 cos(𝑘𝑘𝑘𝑘)
• The constants 𝐴𝐴 and 𝐵𝐵 must be determined by
applying boundary conditions of the particular
situation.
• Plugging into the time part, we get:
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐴𝐴 sin(𝑘𝑘𝑘𝑘) + 𝐵𝐵 cos(𝑘𝑘𝑘𝑘) exp −𝑖𝑖𝑖𝑖𝑖𝑖
• The above can be re-written as: 𝜓𝜓 𝑥𝑥, 𝑡𝑡 =
𝐶𝐶 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖−𝑖𝑖𝑖𝑖𝑖𝑖
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 Wave Mechanics
• B. Particle in a Box or Particle in an Infinite
Potential Energy Well:
• Consider a particle trapped in the region
between 𝑥𝑥 = 0 and 𝑥𝑥 = 𝐿𝐿 by infinitely high
potential energy barriers.
• The potential energy is:
0 for 0 ≤ 𝑥𝑥 ≤ 𝐿𝐿
𝑉𝑉 = � 𝑉𝑉 = 0 𝑉𝑉 = 0 𝑉𝑉 = 0
∞ 𝑥𝑥 < 0, 𝑥𝑥 > 𝐿𝐿

70
 Wave Mechanics
• Because the potential energy is different in the regions
inside and outside the well, we must find separate
solutions in each region.
• For the outside region, we can argue in three ways:
• A. The only way to keep the equation from becoming
meaningless when 𝑉𝑉 → ∞ is to require 𝜓𝜓 = 0, so that
𝑉𝑉𝑉𝑉 will not become infinite.
• B. Alternatively, if the walls at the boundaries of the
well are perfectly rigid, the particle must always be in
the well, and the probability for finding it outside must
be zero.

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 Wave Mechanics
• C. Again, we can think that to get to the outside region,
the particle must surmount a potential barrier that is
infinitely high.
• To overcome such a barrier the particle must have an
infinite amount of energy, which is unphysical. Hence,
the probability for finding it outside must be zero.
• To make the probability zero everywhere outside the
well, we must make 𝜓𝜓 = 0 everywhere outside.
• Thus we have,
𝜓𝜓 𝑥𝑥 = 0, for 𝑥𝑥 < 0, 𝑥𝑥 > 𝐿𝐿

72
 Wave Mechanics
• Inside Region: For the inside region, we have
the solution as in the case of a free particle:
𝜓𝜓 𝑥𝑥 = 𝐴𝐴 sin(𝑘𝑘𝑘𝑘) + 𝐵𝐵 cos(𝑘𝑘𝑘𝑘)
with a 𝑘𝑘 = 2𝑚𝑚𝑚𝑚/ℏ2
• The solution is not yet complete. There are
the arbitrary constants 𝐴𝐴 and 𝐵𝐵.
• Also, we have not got the allowed energy
levels.
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 Wave Mechanics
• Boundary Conditions: To get the arbitrary
constants, we must apply the requirement that
wave function must be continuous across the
boundary:
𝜓𝜓 𝑥𝑥 = 0− = 𝜓𝜓(𝑥𝑥 = 0+ ) At 𝑥𝑥 = 0
lim− 𝜓𝜓(𝑥𝑥) = lim+ 𝜓𝜓(𝑥𝑥) At 𝑥𝑥 = 𝐿𝐿
𝑥𝑥→𝐿𝐿 𝑥𝑥→𝐿𝐿
• Outside the box,
𝜓𝜓 𝑥𝑥 = 0− = 0
lim+ 𝜓𝜓(𝑥𝑥) = 0
𝑥𝑥→𝐿𝐿

74
 Wave Mechanics
• At 𝑥𝑥 = 0, we have:
𝜓𝜓 0 = 𝐴𝐴 sin(0) + 𝐵𝐵 cos(0) = 0
⇒ 𝐵𝐵 = 0
• At 𝑥𝑥 = 𝐿𝐿, we have:
𝜓𝜓 𝐿𝐿 = 𝐴𝐴 sin 𝑘𝑘𝑘𝑘 + 0 = 0
• Since, 𝐴𝐴 ≠ 0, otherwise we get a trivial solution,
we have:
sin 𝑘𝑘𝑘𝑘 = 0
• Hence, 𝑘𝑘𝑘𝑘 = 𝑛𝑛𝑛𝑛, with 𝑛𝑛 = 1,2,3, …
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 Wave Mechanics
• Not all wavelengths are permitted; only
certain values, determined from: 𝑘𝑘𝑘𝑘 = 𝑛𝑛𝑛𝑛
• This is identical with the result obtained in
introductory mechanics for the wavelengths of
the standing waves in a string of length 𝐿𝐿 fixed
at both ends.
Thus the solution to the Schrödinger equation for a
particle trapped in a region of length 𝑳𝑳 by infinite
walls is a series of standing de Broglie waves!

76
 Wave Mechanics
• In terms of the standing de Broglie waves, the
wave function must have a node at the
boundaries at 𝑥𝑥 = 0 and 𝑥𝑥 = 𝐿𝐿.

77
 Wave Mechanics
• Energy Quantization: Because only certain values
of 𝑘𝑘 = 𝑘𝑘𝑛𝑛 are permitted only certain values of 𝐸𝐸
may occur:
ℏ2 𝑘𝑘𝑛𝑛2 ℏ2 𝑛𝑛2 𝜋𝜋 2 ℎ2 𝑛𝑛2
𝐸𝐸𝑛𝑛 = = 2
=
2𝑚𝑚 2𝑚𝑚𝐿𝐿 8𝑚𝑚𝐿𝐿2
𝐸𝐸𝑛𝑛 = 𝑛𝑛2 𝐸𝐸1
• The energy is determined by
the mass of the particle and
the width of the well.

78
 Wave Mechanics
• Wave Functions of a Particle in a Box:
• The wave functions of a particle in a box whose
energies are 𝐸𝐸𝑛𝑛 = ℏ2 𝑘𝑘𝑛𝑛2 /2𝑚𝑚 are:
𝑛𝑛𝑛𝑛
𝜓𝜓 = 𝜓𝜓𝑛𝑛 𝑥𝑥 = 𝐴𝐴 sin(𝑘𝑘𝑛𝑛 𝑥𝑥) = 𝐴𝐴 sin 𝑥𝑥
𝐿𝐿
• These are the eigenfunctions corresponding to the
energy eigenvalues 𝐸𝐸𝑛𝑛 .
• The amplitude of the wave function is found from the
conservation of probability i.e. from normalization as:
𝐿𝐿
� 𝜓𝜓𝑛𝑛 𝑥𝑥 2
𝑑𝑑𝑑𝑑 = 1
0

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 Wave Mechanics
• The same normalization is true for all different
eigen-functions:
𝐿𝐿 2 2 𝐿𝐿 2 𝑛𝑛𝑛𝑛𝑛𝑛
∫0 𝜓𝜓𝑛𝑛 𝑥𝑥 𝑑𝑑𝑑𝑑 = 𝐴𝐴 ∫0 sin 𝑑𝑑𝑑𝑑 = 1
𝐿𝐿
𝐴𝐴2 𝐿𝐿 𝐿𝐿
2𝑛𝑛𝑛𝑛𝑛𝑛
⇒ � 𝑑𝑑𝑑𝑑 − � cos 𝑑𝑑𝑑𝑑 = 1
2 0 0 𝐿𝐿
𝐴𝐴2 𝐿𝐿 2𝜋𝜋𝜋𝜋𝜋𝜋 𝐴𝐴2 𝐿𝐿
⇒ 𝐿𝐿 − sin +0 = =1
2 2𝜋𝜋𝜋𝜋 𝐿𝐿 2
• Hence the normalization constant is 𝐴𝐴 = 2/𝐿𝐿 .

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 Wave Mechanics
• The normalized wave functions are:
𝜓𝜓𝑛𝑛 𝑥𝑥 = 2/𝐿𝐿 sin 𝑛𝑛𝑛𝑛𝑛𝑛/𝐿𝐿

81
 Wave Mechanics
• Example-4: Energy Quantization for a Macroscopic
Object:
• A small object of mass 1.00 mg is confined to move
between two rigid walls separated by 1.00 cm.
• (a) Calculate the minimum speed of the object.
• (b) If the speed of the object is 3.00 cm/s, find the
corresponding value of 𝑛𝑛.
• Solution-4: We consider the object to be a particle
confined in a box.
• Here 𝐿𝐿 = 1.00 cm is the size of the box and 𝑚𝑚 = 1 mg.

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 Wave Mechanics
• Solution-4 (contd.): The quantized energy levels are:
ℏ2 𝑘𝑘𝑛𝑛2 ℏ2 𝑛𝑛2 𝜋𝜋 2 𝑛𝑛2 ℎ2
𝐸𝐸𝑛𝑛 = = 2
=
2𝑚𝑚 2𝑚𝑚𝐿𝐿 8𝑚𝑚𝐿𝐿2
where 𝑛𝑛 = 1,2,3, …
• The minimum energy results from taking 𝑛𝑛 = 1 :
6.626 × 10−34 J.s 2
𝐸𝐸1 =
8 1.0 × 10−6 kg 1.0 × 10−4 m2
= 5.49 × 10−58 J
• This is an incredibly small energy for a macroscopic
particle/object.

83
 Wave Mechanics
• Solution-4 (contd.): Since, the energy is all kinetic, we
have the minimum speed of the object is:
𝑣𝑣1 = 2𝐸𝐸1 /𝑚𝑚 = 2 5.49 × 10−58 J / 1.0 × 10−6 kg
⇒ 𝑣𝑣1 = 3.31 × 10−26 m/s
• This speed is immeasurably small, so that for all
practical purposes the object can be considered to be
at rest.
• Indeed, the time required for an object with this speed
to move the 1.00 cm separating the walls is about
3 × 1023 s, or about 1 million times the present age of
the Universe!

84
 Wave Mechanics
• Solution-4 (contd.): (b) If the speed of the particle is
𝑣𝑣 = 𝑣𝑣𝑛𝑛 = 3.00 cm/s, then its energy is:
1
𝐸𝐸𝑛𝑛 = 𝐾𝐾 = 𝑚𝑚𝑣𝑣 2
2
= 0.5 1.0 × 10−6 kg 3 × 10−2 m/s 2
𝐸𝐸𝑛𝑛 = 4.50 × 10−10 J
• The quantum number 𝑛𝑛 corresponding to this is:
8𝑚𝑚𝐿𝐿2 𝐸𝐸𝑛𝑛 8 × 10−6 kg 1 × 10−4 m2 4.50 × 10−10 J
𝑛𝑛 = =
ℎ 6.626 × 10−34 J.s
⇒ 𝑛𝑛 = 9.05 × 1023

85
 Wave Mechanics
• Solution-4 (contd.): Notice that the quantum number
representing a typical speed for this ordinary-size
object is enormous.
• In fact, the value of 𝑛𝑛 is so large that we would never
be able to distinguish the quantized nature of the
energy levels.
• The difference in energy between two consecutive
states with quantum numbers 𝑛𝑛 = 9.05 × 1023 and
𝑛𝑛 + 1 = 9.05 × 1023 + 1 is very small:
2
ℎ
Δ𝐸𝐸 = 𝑛𝑛 + 1 2 − 𝑛𝑛2 2
≈ 2𝑛𝑛𝐸𝐸1
8𝑚𝑚𝐿𝐿
⇒ Δ𝐸𝐸 ≈ 2 9.05 5.49 × 10−58+23 J ≈ 10−34 J
86
 Wave Mechanics
• Example-5: Find the probability that a particle
trapped in a box 𝐿𝐿 wide can be found between
0.45𝐿𝐿 and 0.55𝐿𝐿 for the ground and first excited
states.
• Solution-5: The relevant part of the box has a
width equal to one-tenth of the box’s width.
• Classically we would expect the particle to be in
this region 10 percent of the time.
• Quantum mechanics gives quite different
predictions that depend on the quantum number
of the particle’s state.
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 Wave Mechanics
• Solution-5(contd.): The probability of finding the particle
between 𝑥𝑥 = 𝑥𝑥1 and 𝑥𝑥 = 𝑥𝑥2 is given by:
𝑥𝑥2
2 𝑑𝑑𝑑𝑑
𝑃𝑃 𝑥𝑥1 ≤ 𝑥𝑥 ≤ 𝑥𝑥2 = 𝑃𝑃𝑥𝑥1,𝑥𝑥2 = � 𝜓𝜓𝑛𝑛 𝑥𝑥
𝑥𝑥1
2 𝑥𝑥2 2 𝑛𝑛𝑛𝑛𝑛𝑛
⇒ 𝑃𝑃𝑥𝑥1,𝑥𝑥2 = � sin 𝑑𝑑𝑑𝑑
𝐿𝐿 𝑥𝑥1 𝐿𝐿
𝑥𝑥2
21 𝐿𝐿 2𝑛𝑛𝑛𝑛𝑛𝑛
⇒ 𝑃𝑃𝑥𝑥1,𝑥𝑥2 = 𝑥𝑥 − sin
𝐿𝐿 2 2𝑛𝑛𝑛𝑛 𝐿𝐿 𝑥𝑥1
𝑥𝑥2 − 𝑥𝑥1 1 2𝑛𝑛𝑛𝑛𝑥𝑥2 2𝑛𝑛𝑛𝑛𝑥𝑥1
⇒ 𝑃𝑃𝑥𝑥1,𝑥𝑥2 = − sin − sin
𝐿𝐿 2𝜋𝜋𝜋𝜋 𝐿𝐿 𝐿𝐿

88
 Wave Mechanics
• Solution-5(contd.): Thus, the probability of finding the
particle in between 𝑥𝑥1 and 𝑥𝑥2 depends on the quantum
number, i.e. on the state.
• For the ground state, which corresponds to 𝑛𝑛 = 1, we
have:
𝑃𝑃𝑥𝑥1,𝑥𝑥2 = 0.198 = 19.8%
which is about twice the classical probability.
• For the first excited state, which corresponds to 𝑛𝑛 = 2,
we have:
𝑃𝑃𝑥𝑥1,𝑥𝑥2 = 0.0065 = 0.65%

89
 Wave Mechanics
• Solution-5(contd.): The low value of finding
the particle in the range
𝑥𝑥 ∈ 𝑥𝑥1 , 𝑥𝑥2 = 0.45𝐿𝐿, 0.55𝐿𝐿
is consistent with the
probability density of
𝜓𝜓2 2 = 0 at 𝑥𝑥 = 0.5𝐿𝐿

90
 Wave Mechanics
• Example-6: A particle is known to be in the
ground state of an infinite square well with
length 𝐿𝐿.
• Calculate the probability that this particle will
be found in the middle half of the well, that is,
between 𝑥𝑥 = 𝐿𝐿/4 and 𝑥𝑥 = 3𝐿𝐿/4.
• Solution-6: The probability density is given by
𝜓𝜓𝑛𝑛 𝑥𝑥 2 with 𝑛𝑛 = 1 for the ground state.
• For 𝑛𝑛 = 1, 𝜓𝜓1 𝑥𝑥 = 2/𝐿𝐿 sin 𝜋𝜋𝜋𝜋/𝐿𝐿
91
 Wave Mechanics
• Solution-6(contd.): Hence,
2 3𝐿𝐿/4 2 𝜋𝜋𝜋𝜋 1 3𝐿𝐿/4 2𝜋𝜋𝜋𝜋
𝑃𝑃 = � sin 𝑑𝑑𝑑𝑑 = � 1 − cos 𝑑𝑑𝑑𝑑
𝐿𝐿 𝐿𝐿/4 𝐿𝐿 𝐿𝐿 𝐿𝐿/4 𝐿𝐿
3𝐿𝐿/4
1 2𝐿𝐿 𝐿𝐿 2𝜋𝜋𝜋𝜋
⇒ 𝑃𝑃 = − sin �
𝐿𝐿 4 2𝜋𝜋 𝐿𝐿 𝐿𝐿
4
1 1 1 1
⇒ 𝑃𝑃 = − −1 − 1 = + = 0.8183
2 2𝜋𝜋 2 𝜋𝜋
• This is considerably larger than, which would be expected
for a classical particle, that spends equal time in all parts of
the well.

92
 Wave Mechanics
• Expectation Values of Operators:
• In quantum mechanics, all real measurable
quantities have a corresponding appropriate
operator representation.
• The wave function contains information about
the behavior of the associated particle in that it
specifies the probability density for the particle.
• Now if an operator acts on the wave function, in
general it will give another wave function:
𝑂𝑂� 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝜓𝜓 ′ (𝑥𝑥, 𝑡𝑡)

93
 Wave Mechanics
• If the wave function happens to be an eigen-function
of the operator, we will get back the original wave
function with some multiplicative factor:
𝑂𝑂� 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑎𝑎 𝜓𝜓(𝑥𝑥, 𝑡𝑡)
• In this case, the multiplicative factor is called the
eigenvalue of the operator 𝑂𝑂� for the particular eigen-
function 𝜓𝜓(𝑥𝑥, 𝑡𝑡)
• For example, for the momentum operator, the free
particle wave function is an eigen-function:
(𝑖𝑖𝑖𝑖𝑖𝑖−𝑖𝑖𝑖𝑖𝑖𝑖)
𝜕𝜕
𝑝𝑝̂ 𝐴𝐴𝑒𝑒 = −𝑖𝑖𝑖 𝐴𝐴𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖−𝑖𝑖𝑖𝑖𝑖𝑖 = ℏ𝑘𝑘𝑘𝑘𝑒𝑒 (𝑖𝑖𝑖𝑖𝑖𝑖−𝑖𝑖𝑖𝑖𝑖𝑖)
𝜕𝜕𝜕𝜕
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 Wave Mechanics
• If a system is in a particular eigenstate of an
operator, then and only then we get an
eigenvalue corresponding to the “value” of
the associated physical quantity.
• However, in general, a system may not be in a
particular eigenstate of an operator.
• Question: Then what value of the physical
quantity we will get if we measure the
quantity?

95
 Wave Mechanics
• Answer: The answer is that we may get any of
the all possible values.
• We can only say that, we will get one
particular eigenvalue about certain number of
times, if we measure many many times.
• That is, we can only tell about the probability
of finding a particular value of the physical
quantity if measured in any general state.

96
 Wave Mechanics
• Average Value of a Quantity: The average value
of a quantity is the mean of the all obtained
values.
• If we get a certain number of values a few times
(i.e. more than once), then we have to take the
weighted average.
• The weighted average value would be:
𝑄𝑄1 𝑓𝑓1 + 𝑄𝑄2 𝑓𝑓2 + ⋯ + 𝑄𝑄𝑛𝑛 𝑓𝑓𝑛𝑛
𝑄𝑄� =
𝑓𝑓1 + 𝑓𝑓2 + ⋯ + 𝑓𝑓𝑛𝑛
where we get the eigenvalue 𝑄𝑄1 , in 𝑓𝑓1 times, etc.

97
 Wave Mechanics
• Now the probability of occurrence is exactly:
𝑓𝑓1
𝑃𝑃1 = 𝑛𝑛
∑𝑖𝑖=1 𝑓𝑓𝑖𝑖
• Hence the average value is (with ∑ 𝑃𝑃𝑖𝑖 = 1):
𝑛𝑛

𝑄𝑄� = � 𝑄𝑄𝑖𝑖 𝑃𝑃𝑖𝑖

𝑖𝑖=1
• This is the expected value of the measurement
of the quantity represented by 𝑄𝑄.
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 Wave Mechanics
• In quantum mechanics, the operator (say 𝑄𝑄� )
corresponding to a quantity (say 𝑄𝑄), will have an
expectation value (expected outcome or average
value of the quantity) IN A PARTICULAR STATE :

�𝑄𝑄�� = � 𝜓𝜓 ∗ (𝑥𝑥) 𝑄𝑄� 𝜓𝜓 𝑥𝑥 𝑑𝑑𝑑𝑑

• Recall that, probability density of finding system

in a particular state is 𝜌𝜌 𝑥𝑥 = 𝜓𝜓 𝑥𝑥 2 = 𝜓𝜓 ∗ 𝜓𝜓

99
 Wave Mechanics
• Note that: �𝑄𝑄�� has the same form as ∑ 𝑃𝑃𝑖𝑖 𝑄𝑄𝑖𝑖
except that:
A. Discrete sum is being replaced by continuous
integration.
B. The operator will act on the wave function to
the right and hence it is inserted in the middle.
C. Furthermore, with this form, we get one
particular eigenvalue as the expectation value in a
particular eigenstate.

100
 Wave Mechanics
• Expectation Value in an Eigenstate:
• For a particular eigenstate i.e. for an eigen-function:
𝑄𝑄� 𝜓𝜓𝑖𝑖 𝑥𝑥 = 𝑄𝑄𝑖𝑖 𝜓𝜓𝑖𝑖 (𝑥𝑥)
• The expectation value in that state is:

�𝑄𝑄� � = � 𝜓𝜓𝑖𝑖∗ (𝑥𝑥)𝑄𝑄� 𝜓𝜓𝑖𝑖 (𝑥𝑥) 𝑑𝑑𝑑𝑑 = 𝑄𝑄𝑖𝑖 � 𝜓𝜓𝑖𝑖 𝑥𝑥 2 𝑑𝑑𝑑𝑑

⇒ �𝑄𝑄� � = 𝑄𝑄𝑖𝑖
• Thus we have a “sharp” expectation value of the operator
in the 𝑖𝑖-th eigenstate.
• This is because in that state no other value can be obtained.

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 Wave Mechanics
• Uncertainty of an Operator: The uncertainty of an
operator is defined in analogy with the standard
deviation of a quantity.
• The standard deviation of a quantity 𝑄𝑄 having possible
values 𝑄𝑄𝑖𝑖 is defined as:
∑𝑖𝑖 𝑄𝑄𝑖𝑖 − 𝑄𝑄� 2
𝜎𝜎𝑄𝑄 =
𝑛𝑛
• But we have:
1 2 1
� 𝑄𝑄𝑖𝑖 − 𝑄𝑄� /𝑛𝑛 = � 𝑄𝑄𝑖𝑖 − 𝑄𝑄� � 𝑄𝑄𝑖𝑖 + 𝑄𝑄� �
2 2 2
𝑖𝑖 𝑛𝑛 𝑛𝑛 𝑛𝑛
𝑖𝑖 𝑖𝑖 𝑖𝑖

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 Wave Mechanics
• Hence,
� 𝑄𝑄𝑖𝑖 − 𝑄𝑄� 2 /𝑛𝑛 = 𝑄𝑄2 − 2𝑄𝑄�𝑄𝑄� + 𝑄𝑄�2 = 𝑄𝑄2 − 𝑄𝑄�2
𝑖𝑖

• Hence, 𝜎𝜎𝑄𝑄 = 𝑄𝑄2 − 𝑄𝑄�2

• Recalling that the average value corresponds to
the expectation value in quantum mechanics, we
may define the uncertainty in 𝑄𝑄� i.e. Δ𝑄𝑄 by :
2
2 � 2
Δ𝑄𝑄 = �𝑄𝑄 � − �𝑄𝑄� �

103
 Wave Mechanics
• Example-7: Compute the average position ⟨𝑥𝑥 ⟩ and
the quantum uncertainty of 𝑥𝑥 i.e. Δ𝑥𝑥 for a
particle in a box, assuming that it is in the ground
state.
• Solution-7: The possible particle positions within
the box are weighted according to the probability
density given by:
2
2 2 𝑛𝑛𝑛𝑛𝑛𝑛
𝜓𝜓𝑛𝑛 𝑥𝑥 = sin
𝐿𝐿 𝐿𝐿
• In the ground state 𝑛𝑛 = 1 , and the average
position is: ⟨𝑥𝑥 ⟩ = ∫ 𝑥𝑥 𝜓𝜓1 𝑥𝑥 2 𝑑𝑑𝑑𝑑
104
 Wave Mechanics
• Solution-7(contd.): Hence we have for 𝑛𝑛 = 1
state:
𝐿𝐿
2
2 2
𝜋𝜋𝜋𝜋
⟨𝑥𝑥⟩ = � 𝑥𝑥 𝜓𝜓1 𝑥𝑥 𝑑𝑑𝑑𝑑 = � 𝑥𝑥 sin 𝑑𝑑𝑑𝑑
𝐿𝐿 0 𝐿𝐿
2𝐿𝐿 𝜋𝜋
⇒ ⟨𝑥𝑥⟩ = 2 � 𝜃𝜃 sin2 𝜃𝜃 𝑑𝑑𝑑𝑑 ,using 𝜃𝜃 = 𝜋𝜋𝜋𝜋/𝐿𝐿
𝜋𝜋 0
2𝐿𝐿 1 𝜋𝜋
⇒ ⟨𝑥𝑥⟩ = 2 � 𝜃𝜃 − 𝜃𝜃 cos 2𝜃𝜃 𝑑𝑑𝑑𝑑
𝜋𝜋 2 0
105
 Wave Mechanics
• Solution-7(contd.): The second integral can be
evaluated by integration by parts:
𝜋𝜋
𝜋𝜋
𝜃𝜃 1
� 𝜃𝜃 cos 2𝜃𝜃 𝑑𝑑𝑑𝑑 = sin 2𝜃𝜃 − � sin 2𝜃𝜃 𝑑𝑑𝑑𝑑
0 2 2
0
1
= cos 2𝜋𝜋 − cos 0 = 0
4
• Hence we get, ⟨𝑥𝑥 ⟩ = 𝐿𝐿/𝜋𝜋 2 𝜋𝜋 2 /2 = 𝐿𝐿/2
• This is an expected result because there is an equal
probability of finding the particle in the left half or the
right half of the box.

106
 Wave Mechanics
• Solution-7(contd.): ⟨𝑥𝑥 2 ⟩ is computed in much the
same way, but with an extra factor of 𝑥𝑥 in the
integrand.
𝐿𝐿 𝐿𝐿
2 2 2
2 2 2
𝜋𝜋𝜋𝜋
⟨𝑥𝑥 ⟩ = � 𝑥𝑥 𝜓𝜓1 𝑥𝑥 𝑑𝑑𝑑𝑑 = � 𝑥𝑥 sin 𝑑𝑑𝑑𝑑
0 𝐿𝐿 0 𝐿𝐿
2 𝜋𝜋 𝜋𝜋
𝐿𝐿
⇒ ⟨𝑥𝑥 2 ⟩ = 3 � 𝜃𝜃 2 𝑑𝑑𝑑𝑑 − � 𝜃𝜃 2 cos 2𝜃𝜃 𝑑𝑑𝑑𝑑
𝜋𝜋 0 0
• The first integral is equal to 𝜋𝜋 3 /3

107
 Wave Mechanics
• Solution-7(contd.): The second integral may be
evaluated by integration by parts:
𝜋𝜋 𝜋𝜋
� 𝜃𝜃 2 cos 2𝜃𝜃 𝑑𝑑𝑑𝑑 = 0 − � 𝜃𝜃 sin 2𝜃𝜃 𝑑𝑑𝑑𝑑
0 0
1 𝜋𝜋 𝜋𝜋
= 𝜃𝜃 cos 2𝜃𝜃� =
2 0 2
• Hence, we get
2 3 2 2
𝐿𝐿 𝜋𝜋 𝜋𝜋 𝐿𝐿 𝐿𝐿
⟨𝑥𝑥 2 ⟩ = 3 − = − 2
𝜋𝜋 3 2 3 2𝜋𝜋
108
 Wave Mechanics
• Solution-7(contd.): Hence the uncertainty in the
position is:
1 1 1
Δ𝑥𝑥 = ⟨𝑥𝑥 2 ⟩ − ⟨𝑥𝑥 ⟩2 = 𝐿𝐿 − 2 − = 0.181𝐿𝐿
3 2𝜋𝜋 4
• This is an appreciable figure, amounting to nearly one-
fifth the size of the box.
• Consequently, the whereabouts of such a particle are
largely unknown.
• Also note that these expectation values are time-
independent.
109
 Wave Mechanics
• Example-8: Show that the expectation value of the
momentum operator in any state of a particle in an one
dimensional box vanishes.
• Solution-8: For particle in a box, the wave function is:
2 𝑛𝑛𝑛𝑛𝑛𝑛
𝜓𝜓𝑛𝑛 𝑥𝑥 = sin
𝐿𝐿 𝐿𝐿
• The momentum expectation value is:
𝐿𝐿
2 𝑛𝑛𝑛𝑛𝑛𝑛 𝑑𝑑 𝑛𝑛𝑛𝑛𝑛𝑛
⟨𝑝𝑝̂ ⟩ = � sin (−𝑖𝑖)ℏ sin 𝑑𝑑𝑑𝑑
𝐿𝐿 0 𝐿𝐿 𝑑𝑑𝑑𝑑 𝐿𝐿

110
 Wave Mechanics
• Solution-8 (contd.) : Hence, we have
𝐿𝐿
2 𝑛𝑛𝑛𝑛 𝑛𝑛𝑛𝑛𝑛𝑛 𝑛𝑛𝑛𝑛𝑛𝑛
⟨𝑝𝑝̂ ⟩ = −𝑖𝑖𝑖 � sin cos 𝑑𝑑𝑑𝑑
𝐿𝐿 𝐿𝐿 0 𝐿𝐿 𝐿𝐿
𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝐿𝐿 2𝑛𝑛𝑛𝑛𝑛𝑛
⇒ ⟨𝑝𝑝̂ ⟩ = − 2 � sin 𝑑𝑑𝑑𝑑
𝐿𝐿 0 𝐿𝐿
𝐿𝐿
𝑖𝑖𝑖𝑖𝑖𝑖𝑖 𝐿𝐿 2𝑛𝑛𝑛𝑛𝑛𝑛
⇒ ⟨𝑝𝑝̂ ⟩ = 2 cos =0
𝐿𝐿 2𝑛𝑛𝑛𝑛 𝐿𝐿 0
• Physically, the expectation value or the average value
of the momentum of the particle must be zero.

111
 Wave Mechanics
• Solution-8 (contd.) : This is because the particle
must be bouncing back and forth between the
ends of the region and constantly reversing the
sign (i.e., the direction) of its momentum.
• The magnitude of its momentum must be such
that 𝑝𝑝2 /2𝑚𝑚 = 𝐸𝐸.
• But since it is equally probable that the sign of
the momentum will be either positive or
negative, measurements of this quantity will
average out to zero.
112
 Wave Mechanics
• Example-9: Are the stationary states of the 1D infinite
square well potential eigenvalues of 𝑝𝑝̂ or 𝑝𝑝̂ 2 ?
• If so, what are the eigenvalues? Discuss the
implications of these results.
• Solution-9: The wave-functions for the stationary states
in a particle inside an 1D infinite well are:
2 𝑛𝑛𝑛𝑛𝑛𝑛 −𝑖𝑖𝜔𝜔 𝑡𝑡
𝜓𝜓𝑖𝑖 𝑥𝑥, 𝑡𝑡 = sin 𝑒𝑒 𝑛𝑛
𝐿𝐿 𝐿𝐿
where ℏ𝜔𝜔𝑛𝑛 = 𝐸𝐸𝑛𝑛 = 𝑛𝑛2 ℎ2 / 8𝑚𝑚𝐿𝐿2 are the energy
eigenvalues

113
 Wave Mechanics
• Solution-9 (contd.): Testing for the eigenvalue, we
get (using 𝜓𝜓𝑖𝑖 𝑥𝑥, 𝑡𝑡 = 𝜓𝜓𝑖𝑖 𝑥𝑥 𝑓𝑓 𝑡𝑡 , 𝑖𝑖 = 𝑛𝑛):
𝜕𝜕 2 𝑛𝑛𝑛𝑛 𝑛𝑛𝑛𝑛
𝑝𝑝̂ 𝜓𝜓𝑖𝑖 (𝑥𝑥) = −𝑖𝑖𝑖 𝜓𝜓𝑖𝑖 (𝑥𝑥) = −𝑖𝑖𝑖 cos 𝑥𝑥
𝜕𝜕𝜕𝜕 𝐿𝐿 𝐿𝐿 𝐿𝐿
• Hence we see at once that the operator 𝑝𝑝̂ does
not return the original function 𝜓𝜓𝑖𝑖 𝑥𝑥, 𝑡𝑡 .
• Hence, the stationary states are not the
eigenstates of the momentum operator.

114
 Wave Mechanics
• Solution-9 (contd.): However, we see, for the operator
𝑝𝑝�2 ≡ −𝑖𝑖𝑖 2 𝜕𝜕 2 /𝜕𝜕𝑥𝑥 2 :
𝜕𝜕 2 2 𝑛𝑛𝑛𝑛
2
𝑝𝑝� 𝜓𝜓𝑖𝑖 𝑥𝑥 = −ℏ2
2
sin 𝑥𝑥
𝜕𝜕𝑥𝑥 𝐿𝐿 𝐿𝐿
2
2 𝑛𝑛2 𝜋𝜋 2 𝑛𝑛𝑛𝑛 𝑛𝑛𝑛𝑛𝑛
𝑝𝑝�2 𝜓𝜓𝑖𝑖 𝑥𝑥 = −ℏ2 −1 sin 𝑥𝑥 = 𝜓𝜓𝑖𝑖 𝑥𝑥
𝐿𝐿 𝐿𝐿2 𝐿𝐿 𝐿𝐿
• Hence the eigenvalue of the momentum-squared operator
is :
𝑛𝑛2 𝜋𝜋 2 ℏ2 𝑛𝑛2 ℎ2 𝑛𝑛2 ℎ2
2
= 2
= 2
2𝑚𝑚 = 2𝑚𝑚𝐸𝐸𝑛𝑛
𝐿𝐿 4𝐿𝐿 8𝑚𝑚𝐿𝐿

115
 Wave Mechanics
• Solution-9 (contd.): Since, 𝜓𝜓𝑖𝑖 (𝑥𝑥, 𝑡𝑡) are eigenstates of
the momentum-squared operator, repeated
measurements of 𝑝𝑝̂ 2 for the state labeled by n will give
identical results equal to 𝑛𝑛𝜋𝜋𝜋/𝐿𝐿 2 .
• By contrast, the momentum itself is not a sharp
observable, meaning that different values for 𝑝𝑝̂ will be
obtained in successive measurements.
• In particular, it is the sign or direction of momentum
that is fuzzy, consistent with the classical notion of a
particle bouncing back and forth between the walls of
the “box.”

116
 Wave Mechanics
• Example-10: Show that the uncertainty principle is satisfied
in the stationary states of the particle in a one-dimensional
box.
• Solution-10: We have seen that, for particle in an infinite
1D square potential well of width 𝐿𝐿, the average values of
the position and position-squared are:
⟨𝑥𝑥 ⟩ = 𝐿𝐿/2
𝐿𝐿2 𝐿𝐿2
⟨𝑥𝑥 2 ⟩ = − 2
3 2𝜋𝜋
• The uncertainty in position is defined as:

Δ𝑥𝑥 = ⟨𝑥𝑥 2 ⟩ − ⟨𝑥𝑥 ⟩2

117
 Wave Mechanics
• Solution-10 (contd.): Hence, we get
𝐿𝐿2 𝐿𝐿2 𝐿𝐿2 1 1
Δ𝑥𝑥 = − 2 − = 𝐿𝐿 − 2
3 2𝜋𝜋 4 12 2𝜋𝜋
• Again, the average value of the momentum
operator vanishes : ⟨𝑝𝑝⟩ = 0
• The average value of the momentum squared is:
𝐿𝐿 2
𝜕𝜕
⟨𝑝𝑝2 ⟩ = � 𝜓𝜓𝑖𝑖∗ 𝑥𝑥, 𝑡𝑡 −𝑖𝑖𝑖 2 2 𝜓𝜓𝑖𝑖 𝑥𝑥, 𝑡𝑡 𝑑𝑑𝑑𝑑
0 𝜕𝜕𝑥𝑥
118
 Wave Mechanics
• Solution-10 (contd.): But 𝜓𝜓𝑖𝑖 𝑥𝑥, 𝑡𝑡 is an eigenstate
of the momentum-squared operator with
eigenvalue 2𝑚𝑚 𝐸𝐸𝑛𝑛 = 𝑛𝑛𝜋𝜋𝜋/𝐿𝐿 2 i.e.:
2 2
2
𝜕𝜕 𝑛𝑛𝑛𝑛𝑛
−𝑖𝑖𝑖 2
𝜓𝜓𝑖𝑖 𝑥𝑥, 𝑡𝑡 = 𝜓𝜓𝑖𝑖 (𝑥𝑥, 𝑡𝑡)
𝜕𝜕𝑥𝑥 𝐿𝐿
• Hence, we get using the normalization
𝐿𝐿
∫0 𝜓𝜓𝑖𝑖 2 𝑑𝑑𝑑𝑑 = 1 :
2 𝐿𝐿 2
2
𝑛𝑛𝑛𝑛𝑛 ∗ 𝑛𝑛𝑛𝑛𝑛
⟨𝑝𝑝 ⟩ = � 𝜓𝜓𝑖𝑖 𝑥𝑥, 𝑡𝑡 𝜓𝜓𝑖𝑖 𝑥𝑥, 𝑡𝑡 𝑑𝑑𝑑𝑑 =
𝐿𝐿 0 𝐿𝐿
119
 Wave Mechanics
• Solution-10 (contd.): Hence, the uncertainty in
the momentum is:
Δ𝑝𝑝 = ⟨𝑝𝑝2 ⟩ − ⟨𝑝𝑝⟩2 = 𝑛𝑛𝑛𝑛𝑛/𝐿𝐿 2 − 0 = 𝑛𝑛𝑛𝑛𝑛/𝐿𝐿
• Hence the product of the position and
momentum uncertainties is:
𝐿𝐿 𝑛𝑛𝑛𝑛𝑛 𝑛𝑛𝑛𝑛𝑛 ℏ
Δ𝑥𝑥 Δ𝑝𝑝 = = ≥
2 𝐿𝐿 2 2
• The minimum uncertainty product occurs at
𝑛𝑛 = 1 level and is equal to 𝜋𝜋𝜋/2 = ℎ/4
120
 Wave Mechanics
• C. Two-Dimensional Infinite Potential Energy Well:
• We can extend the calculation of energy eigenvalues
and wave function determination for the particle in a
box, to two and three dimensions.
• The principal features of the solution remain the same,
but an important new feature is introduced which is
called degeneracy.
• Degeneracy: Degeneracy is the phenomenon of having
the same energy (or any physical quantity) in two or
more different states of a system.

121
 Wave Mechanics
• For example, in hydrogen atom, for a given 𝑛𝑛, all the
states corresponding to 𝑙𝑙 = 0,1, … (𝑛𝑛 − 1) have the
same energy and are degenerate.
• The time-independent Schrödinger equation for a
particle confined in a two-dimensional box is:
ℏ2 𝜕𝜕 2 𝜕𝜕 2
− 2
+ 2 𝜓𝜓 𝑥𝑥, 𝑦𝑦 + 𝑉𝑉 𝑥𝑥, 𝑦𝑦 𝜓𝜓 𝑥𝑥, 𝑦𝑦
2𝑚𝑚 𝜕𝜕𝑥𝑥 𝜕𝜕𝑦𝑦
= 𝐸𝐸𝐸𝐸(𝑥𝑥, 𝑦𝑦)
• The two-dimensional well is defined as:
0 for 0 ≤ 𝑥𝑥 ≤ 𝐿𝐿, 0 ≤ 𝑦𝑦 ≤ 𝐿𝐿
𝑉𝑉 𝑥𝑥, 𝑦𝑦 = �
∞ otherwise

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 Wave Mechanics
• The particle is confined by infinitely high barriers
to a square region.
• Outside Solution: The outside solution is zero for
the wave function as the particle does not have
enough energy to overcome the potential barrier.
• Inside Solution: Since the 𝑥𝑥 and 𝑦𝑦 derivatives
appear on equal footing, we can assume a
variable separable solution of the form:
𝜓𝜓 𝑥𝑥, 𝑦𝑦 = 𝑓𝑓(𝑥𝑥)𝑔𝑔(𝑦𝑦)
123
 Wave Mechanics
• For the inside region, we get:
ℏ2 𝑑𝑑 2 𝑓𝑓 𝑥𝑥 𝑑𝑑 2 𝑔𝑔 𝑦𝑦
− 𝑔𝑔 𝑦𝑦 2
+ 𝑓𝑓 𝑥𝑥 2
+0
2𝑚𝑚 𝑑𝑑𝑥𝑥 𝑑𝑑𝑦𝑦
= 𝐸𝐸𝐸𝐸(𝑥𝑥)𝑔𝑔(𝑦𝑦)
1 𝑑𝑑 2 𝑓𝑓 𝑥𝑥 2𝑚𝑚𝑚𝑚 1 𝑑𝑑 2 𝑔𝑔 𝑦𝑦
⇒ 2
=− 2 −
𝑓𝑓 𝑥𝑥 𝑑𝑑𝑥𝑥 ℏ 𝑔𝑔 𝑦𝑦 𝑑𝑑𝑦𝑦 2
• Again, the right hand side is a function of 𝑦𝑦 only
while the left hand side is a function of 𝑥𝑥 only.
• Hence both sides must be constant functions.
124
 Wave Mechanics
• Hence, we have, with the choice of constants:
1 𝑑𝑑2 𝑓𝑓 𝑥𝑥 2
= −𝑘𝑘𝑥𝑥
𝑓𝑓 𝑥𝑥 𝑑𝑑𝑥𝑥 2
2𝑚𝑚𝑚𝑚 1 𝑑𝑑2 𝑔𝑔 𝑦𝑦 2
− 2 − = −𝑘𝑘𝑥𝑥
ℏ 𝑔𝑔 𝑦𝑦 𝑑𝑑𝑦𝑦 2
1 𝑑𝑑2 𝑔𝑔 𝑦𝑦 2
⇒ = −𝑘𝑘 𝑦𝑦
𝑔𝑔 𝑦𝑦 𝑑𝑑𝑦𝑦 2
where
−𝑘𝑘𝑦𝑦2 = −2𝑚𝑚𝑚𝑚/ℏ2 + 𝑘𝑘𝑥𝑥2
⇒ 𝐸𝐸 = ℏ2 𝑘𝑘𝑥𝑥2 + 𝑘𝑘𝑦𝑦2 /2𝑚𝑚

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 Wave Mechanics
• Each of the equations in 𝑥𝑥 and 𝑦𝑦 has the form of the
equation of a simple harmonic motion.
• Hence we have the solution:
𝜓𝜓 𝑥𝑥, 𝑦𝑦 = 𝑓𝑓 𝑥𝑥 𝑔𝑔 𝑦𝑦
= 𝐴𝐴 sin 𝑘𝑘𝑥𝑥 𝑥𝑥 + 𝐵𝐵 cos 𝑘𝑘𝑥𝑥 𝑥𝑥 × 𝐶𝐶 sin 𝑘𝑘𝑦𝑦 𝑦𝑦 + 𝐷𝐷 cos 𝑘𝑘𝑦𝑦 𝑦𝑦
• The particular values of 𝑘𝑘𝑥𝑥 and 𝑘𝑘𝑦𝑦 will be found from
the boundary conditions.
• Boundary Conditions: The continuity condition on
𝜓𝜓(𝑥𝑥, 𝑦𝑦) requires that the solutions inside and outside
match at the boundary.

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 Wave Mechanics
• Because 𝜓𝜓 = 0 everywhere outside, the continuity
condition then requires that 𝜓𝜓 = 0 everywhere on the
boundary:
𝜓𝜓 0, 𝑦𝑦 = 0, 𝜓𝜓 𝐿𝐿, 𝑦𝑦 = 0
𝜓𝜓 𝑥𝑥, 0 = 0, 𝜓𝜓 𝑥𝑥, 𝐿𝐿 = 0
• Boundary at 𝒙𝒙 = 𝟎𝟎 : The condition at 𝑥𝑥 = 0 gives:
𝜓𝜓 0, 𝑦𝑦 = 𝐵𝐵 𝐶𝐶 sin 𝑘𝑘𝑦𝑦 𝑦𝑦 + 𝐷𝐷 cos 𝑘𝑘𝑦𝑦 𝑦𝑦 = 𝑓𝑓 0 𝑔𝑔 𝑦𝑦 = 0
• Hence, 𝑓𝑓(0) = 0 which requires 𝐵𝐵 = 0.
• Boundary at 𝒚𝒚 = 𝟎𝟎 : The condition at 𝑦𝑦 = 0 gives:
𝜓𝜓 𝑥𝑥, 0 = 𝐴𝐴 sin 𝑘𝑘𝑥𝑥 𝑥𝑥 + 𝐵𝐵 cos 𝑘𝑘𝑥𝑥 𝑥𝑥 𝐷𝐷 = 𝑓𝑓 𝑥𝑥 𝑔𝑔 0 = 0
• Hence, 𝑔𝑔(0) = 0, which requires 𝐷𝐷 = 0.
127
 Wave Mechanics
• Boundary at 𝒙𝒙 = 𝑳𝑳 : The condition at 𝑥𝑥 = 𝐿𝐿 gives
(with 𝐵𝐵 = 𝐷𝐷 = 0) :
𝜓𝜓 𝐿𝐿, 𝑦𝑦 = 𝐴𝐴 sin 𝑘𝑘𝑥𝑥 𝐿𝐿 𝐶𝐶 sin 𝑘𝑘𝑦𝑦 𝑦𝑦 = 𝑓𝑓 𝐿𝐿 𝑔𝑔 𝑦𝑦 = 0
• Hence, 𝑓𝑓(𝐿𝐿) = 0, which requires that:
sin(𝑘𝑘𝑥𝑥 𝐿𝐿) = 0
• Thus 𝑘𝑘𝑥𝑥 𝐿𝐿 must be an integer multiple of 𝜋𝜋 ( with
𝑛𝑛𝑥𝑥 = 1,2, …):
𝑘𝑘𝑥𝑥 𝐿𝐿 = 𝑛𝑛𝑥𝑥 𝜋𝜋
𝑛𝑛𝑥𝑥 𝜋𝜋
⇒ 𝑘𝑘𝑥𝑥 =
𝐿𝐿
128
 Wave Mechanics
• Boundary at 𝒚𝒚 = 𝑳𝑳 : The condition at 𝑦𝑦 = 𝐿𝐿 gives
(with 𝐵𝐵 = 𝐷𝐷 = 0) :
𝜓𝜓 𝑥𝑥, 𝐿𝐿 = 𝐴𝐴 sin 𝑘𝑘𝑥𝑥 𝑥𝑥 𝐶𝐶 sin 𝑘𝑘𝑦𝑦 𝐿𝐿 = 𝑓𝑓 𝑥𝑥 𝑔𝑔 𝐿𝐿 = 0
• Hence, g(𝐿𝐿) = 0, which requires that:
sin(𝑘𝑘𝑦𝑦 𝐿𝐿) = 0
• Thus that 𝑘𝑘𝑦𝑦 𝐿𝐿 must be an integer multiple of 𝜋𝜋 (
with 𝑛𝑛𝑦𝑦 = 1,2, …):
𝑘𝑘𝑦𝑦 𝐿𝐿 = 𝑛𝑛𝑦𝑦 𝜋𝜋
𝑛𝑛𝑦𝑦 𝜋𝜋
⇒ 𝑘𝑘𝑦𝑦 =
𝐿𝐿
129
 Wave Mechanics
• Hence we get:
𝑛𝑛𝑥𝑥 𝜋𝜋𝜋𝜋 𝑛𝑛𝑦𝑦 𝜋𝜋𝑦𝑦
𝜓𝜓 𝑥𝑥, 𝑦𝑦 = 𝐴𝐴′ sin sin
𝐿𝐿 𝐿𝐿

130
 Wave Mechanics
• Normalization: The unknown amplitude is found
from the normalization (conservation of
probability):
2
� 𝜓𝜓 𝑥𝑥, 𝑦𝑦 𝑑𝑑𝑑𝑑 𝑑𝑑𝑑𝑑 = 1

• Hence, we get
𝐿𝐿 𝐿𝐿 𝑛𝑛𝑦𝑦 𝜋𝜋𝜋𝜋
′2 2
𝑛𝑛𝑥𝑥 𝜋𝜋𝜋𝜋 2
𝐴𝐴 � 𝑑𝑑𝑑𝑑 � 𝑑𝑑𝑑𝑑 sin sin =1
0 0 𝐿𝐿 𝐿𝐿
• A little bit of calculation gives, 𝐴𝐴′ = 2/𝐿𝐿

131
 Wave Mechanics
• Hence the full wave function is:
2 𝑛𝑛𝑥𝑥 𝜋𝜋𝜋𝜋 𝑛𝑛𝑦𝑦 𝜋𝜋𝜋𝜋
𝜓𝜓 𝑥𝑥, 𝑦𝑦 = sin sin
𝐿𝐿 𝐿𝐿 𝐿𝐿
• Quantization of Energy: The energy eigenvalue is:
ℏ2 𝑘𝑘𝑥𝑥2 + 𝑘𝑘𝑦𝑦2 ℏ2 𝜋𝜋 2 2 2 =
ℎ 2
2 + 𝑛𝑛2
𝐸𝐸 = = 𝑛𝑛 + 𝑛𝑛 𝑛𝑛
2𝑚𝑚 2𝑚𝑚𝐿𝐿2 𝑥𝑥 𝑦𝑦
8𝑚𝑚𝐿𝐿2 𝑥𝑥 𝑦𝑦

where 𝑛𝑛𝑥𝑥 , 𝑛𝑛𝑦𝑦 = 1,2,3, …

• Writing the ground state energy as 𝐸𝐸0 = ℎ2 /8𝑚𝑚𝐿𝐿2 , we
get: 𝐸𝐸 = 𝐸𝐸0 𝑛𝑛𝑥𝑥2 + 𝑛𝑛𝑦𝑦2

132
 Wave Mechanics
• Degeneracy in Energy Levels:
• The energy eigenvalues
have the same value
for more than one
sets of integers (𝑛𝑛𝑥𝑥 , 𝑛𝑛𝑦𝑦 ).
• This is called the degeneracy
in energy.

133
 Wave Mechanics
• Example-A: For example, the energy level at
𝐸𝐸 = 13𝐸𝐸0 is degenerate, because both (𝑛𝑛𝑥𝑥 = 2,
𝑛𝑛𝑦𝑦 = 3) and (𝑛𝑛𝑥𝑥 = 3, 𝑛𝑛𝑦𝑦 = 2) have 𝐸𝐸 = 13𝐸𝐸0 .
• This degeneracy arises from interchanging 𝑛𝑛𝑥𝑥 and
𝑛𝑛𝑦𝑦 (which is the same as interchanging the 𝑥𝑥 and
𝑦𝑦 axes), so the probability distributions in the two
cases are not very different.
• Hence 𝐸𝐸 = 13𝐸𝐸0 level is two-fold degenerate.

134
 Wave Mechanics
• Example-B: For 𝐸𝐸 = 50𝐸𝐸0 , there are three sets of
quantum numbers:
𝑛𝑛𝑥𝑥 = 7,𝑛𝑛𝑦𝑦 = 1; 𝑛𝑛𝑥𝑥 = 1,𝑛𝑛𝑦𝑦 = 7; 𝑛𝑛𝑥𝑥 = 5,𝑛𝑛𝑦𝑦 = 5;
• The first two sets of quantum numbers result
from the interchange of 𝑛𝑛𝑥𝑥 and 𝑛𝑛𝑦𝑦 and so have
similar probability distributions.
• The third state represents a very different state of
motion.
• Hence 𝐸𝐸 = 50𝐸𝐸0 level is thee-fold degenerate.

135
 Wave Mechanics
• Example-11: A particle is confined to a two-
dimensional box of length 𝐿𝐿 and width 2𝐿𝐿. The
energy values are:
ℏ2 𝜋𝜋 2 2 2 2 2
𝐸𝐸 = 2
𝑛𝑛𝑥𝑥 + 𝑛𝑛𝑦𝑦 /4 = 𝐸𝐸 𝑛𝑛
0 𝑥𝑥 + 𝑛𝑛𝑦𝑦 /4
2𝑚𝑚𝐿𝐿
Find the two lowest degenerate levels.
• Solution-11: The possible values of the
quantum numbers are: 𝑛𝑛𝑥𝑥 , 𝑛𝑛𝑦𝑦 = 1,2,3,4, …

136
 Wave Mechanics
• Solution-11 (contd.): Hence, we see in the
following table of 𝑛𝑛𝑥𝑥2 + 𝑛𝑛𝑦𝑦2 /4 for different
values of 𝑛𝑛𝑥𝑥 and 𝑛𝑛𝑦𝑦 :
𝑛𝑛𝑥𝑥 or 𝑛𝑛𝑦𝑦 𝑛𝑛𝑦𝑦 = 1 𝑛𝑛𝑦𝑦 = 2 𝑛𝑛𝑦𝑦 = 3 𝑛𝑛𝑦𝑦 = 4 𝑛𝑛𝑦𝑦 = 5 𝑛𝑛𝑦𝑦 = 6
𝑛𝑛𝑥𝑥 = 1 1 + 1/4 1+1 1 + 9/4 𝟏𝟏 + 𝟒𝟒 1 + 25/4 𝟏𝟏 + 𝟗𝟗
𝑛𝑛𝑥𝑥 = 2 4 + 1/4 𝟒𝟒 + 𝟏𝟏 4 + 9/4 4+4 4 + 25/4 4+9
𝑛𝑛𝑥𝑥 = 3 9 + 1/4 𝟗𝟗 + 𝟏𝟏 9 + 9/4 9+4 9 + 25/4 9+9
𝑛𝑛𝑥𝑥 = 4 16 + 1/4 16 + 1 16 + 9/4 16 + 4 16 + 25/4 16 + 9
𝑛𝑛𝑥𝑥 = 5 25 + 1/4 25 + 1 25 + 9/4 25 + 4 25 + 25/4 25 + 9
𝑛𝑛𝑥𝑥 = 6 36 + 1/4 36 + 1 36 + 9/4 36 + 4 36 + 25/4 36 + 9

The lowest two degenerate states correspond to the

energies: 5𝐸𝐸0 and 10𝐸𝐸0 . 137
 Wave Mechanics
• D. Finite Potential Well:
• Potential energies are never infinite in the real
world, and a box with infinitely hard walls has
no physical counterpart.
• Hence, we expect potential wells with barriers
of finite height to exist.
• Consider a potential well with square corners
that is 𝑈𝑈0 high and 𝐿𝐿 wide and contains a
particle whose energy 𝐸𝐸 is less than 𝑈𝑈0 .
138
 Wave Mechanics
• According to classical mechanics, when the
particle strikes the sides of the well, it
bounces off without entering regions I and III.
• However in quantum
theory there is a finite 𝑈𝑈 = 𝑈𝑈 𝑈𝑈 = 𝑈𝑈0
0
non-zero probability
of finding the particle
in regions I and III.
139
 Wave Mechanics
• Outside Regions: In regions I and III we have:
𝑑𝑑 2 𝜓𝜓 2𝑚𝑚
2
+ 2 𝐸𝐸 − 𝑈𝑈0 𝜓𝜓 = 0
𝑑𝑑𝑥𝑥 ℏ
𝑑𝑑 2 𝜓𝜓 2
⇒ 2
− 𝛼𝛼 𝜓𝜓 = 0
𝑑𝑑𝑥𝑥
2𝑚𝑚 𝑈𝑈0 −𝐸𝐸
where 𝛼𝛼 = is real for 𝐸𝐸 < 𝑈𝑈0 .
ℏ
• The solutions of the above equation are:
𝜓𝜓𝐼𝐼 = 𝐶𝐶𝑒𝑒 𝛼𝛼𝛼𝛼 + 𝐷𝐷𝑒𝑒 −𝛼𝛼𝛼𝛼 𝑥𝑥 < 0
𝜓𝜓𝐼𝐼𝐼𝐼𝐼𝐼 = 𝐹𝐹𝑒𝑒 𝛼𝛼𝛼𝛼 + 𝐺𝐺𝑒𝑒 −𝛼𝛼𝛼𝛼 𝑥𝑥 > 𝐿𝐿

140
 Wave Mechanics
• Inside Region: Within the well Schrödinger equation is
the same as that for a free particle.
• Hence the solution of Schrödinger equation is:
2𝑚𝑚𝑚𝑚 2𝑚𝑚𝑚𝑚
𝜓𝜓𝐼𝐼𝐼𝐼 𝑥𝑥 = 𝐴𝐴 sin 𝑥𝑥 + 𝐵𝐵 cos 𝑥𝑥
ℏ ℏ
• The arbitrary constants 𝐴𝐴, 𝐵𝐵, 𝐶𝐶, 𝐷𝐷 must be found from
boundary and normalization conditions.
• Boundary Conditions:
• A. At the boundaries at 𝑥𝑥 → ±∞ the wave function
must be finite and zero. The probability of finding the
particle at 𝑥𝑥 → ±∞ must be zero.

141
 Wave Mechanics
• B. Furthermore, both 𝜓𝜓(𝑥𝑥) and 𝑑𝑑𝑑𝑑(𝑥𝑥)/𝑑𝑑𝑑𝑑 must be
continuous at the well boundary 𝑥𝑥 = 0 and 𝑥𝑥 = 𝐿𝐿.
• This is because the wave functions inside and outside
each side of the well:
(A) must not only have the same value where they join
(B) but also the same slope, so they match up perfectly.
• This can be done only for certain values of 𝐸𝐸 ,
corresponding to the allowed energies for the bound
particle.

142
 Wave Mechanics
• Boundaries at 𝒙𝒙 → ±∞:
• Both 𝜓𝜓𝐼𝐼 and 𝜓𝜓𝐼𝐼𝐼𝐼𝐼𝐼 must be finite everywhere to be
physically meaningful.
• Since exp −𝛼𝛼𝛼𝛼 → ∞ as 𝑥𝑥 → −∞, and exp 𝛼𝛼𝛼𝛼 → ∞
as 𝑥𝑥 → ∞, we must have 𝐷𝐷 = 𝐹𝐹 = 0.
• Hence, we have 𝑥𝑥 < 0
𝜓𝜓𝐼𝐼 = 𝐶𝐶𝑒𝑒 𝛼𝛼𝛼𝛼
−𝛼𝛼𝛼𝛼
𝑥𝑥 > 𝐿𝐿
𝜓𝜓𝐼𝐼𝐼𝐼𝐼𝐼 = 𝐺𝐺𝑒𝑒
• These wave functions decrease exponentially inside the
barriers on both sides away from the wall.

143
 Wave Mechanics
• Boundaries at 𝒙𝒙 = 𝟎𝟎, 𝑳𝑳:
• Here, boundary conditions are:
𝜓𝜓𝐼𝐼𝐼𝐼 𝑥𝑥 = 0 = 𝐶𝐶 = 𝐵𝐵
𝜓𝜓𝐼𝐼𝐼𝐼 𝑥𝑥 = 𝐿𝐿 = 𝐺𝐺𝑒𝑒 −𝛼𝛼𝐿𝐿 = 𝐴𝐴 sin 𝑘𝑘 𝐿𝐿 + 𝐵𝐵 cos 𝑘𝑘𝐿𝐿
where 𝑘𝑘 = 2𝑚𝑚𝑚𝑚/ℏ
• The fact that the wave function 𝜓𝜓𝐼𝐼𝐼𝐼𝐼𝐼 is nonzero at
the walls increases the de Broglie wavelength in
the well (compared with that in the infinite well).
• This in turn lowers the energy and momentum of
the particle.

144
 Wave Mechanics
• The wave function and the probability
densities are shown below:

145
 Wave Mechanics
• Penetration Depth 𝜹𝜹 : The wave function
penetrates the exterior region on a scale of
length set by the penetration depth , given by:
1 ℏ
𝛿𝛿 = =
𝛼𝛼 2𝑚𝑚(𝑈𝑈0 − 𝐸𝐸 )
• At a distance 𝛿𝛿 beyond the
well-edge, the wave amplitude
has fallen to 1/𝑒𝑒 of its value
at the edge.
146
 Wave Mechanics
• Energy Quantization:
• A. Approximate Treatment: The wave function
approaches zero exponentially in the exterior region
and at 𝛿𝛿 its amplitude decreases to 1/𝑒𝑒 of its value at
the edge.
• Considering that the exterior wave function is
essentially zero beyond 𝛿𝛿 distance, the allowed
energies would be those for an infinite well of length
𝐿𝐿 + 2𝛿𝛿:
ℏ2 𝑛𝑛2 𝜋𝜋 2
𝐸𝐸𝑛𝑛 ≈ 2 𝑛𝑛 = 1,2, …
2𝑚𝑚 𝐿𝐿 + 2𝛿𝛿
147
 Wave Mechanics
• However, 𝛿𝛿 = ℏ/ 2𝑚𝑚(𝑈𝑈0 − 𝐸𝐸 ), itself depends
on energy 𝐸𝐸 = 𝐸𝐸𝑛𝑛 and hence the above is an
implicit relation for 𝐸𝐸 that must be solved
numerically for a given value of 𝑛𝑛.
• This approximation is best for the lowest-lying
states and breaks down completely as 𝐸𝐸
approaches 𝑈𝑈0 , i.e. where 𝛿𝛿 becomes infinite.
• From this we infer that the number of bound
states is limited by the height 𝑼𝑼𝟎𝟎 of our potential
well.
148
 Wave Mechanics
• The penetration distance increases as we go
up in energy.

The probability densities of the four states in the one-dimensional

potential energy well of width 0.100 nm and depth 400 eV. 149
 Wave Mechanics
• B. Exact Treatment: The wave functions in the three
regions are:
𝜓𝜓𝐼𝐼 = 𝐶𝐶𝑒𝑒 𝛼𝛼𝛼𝛼
𝜓𝜓𝐼𝐼𝐼𝐼𝐼𝐼 = 𝐺𝐺𝑒𝑒 −𝛼𝛼𝛼𝛼
2𝑚𝑚𝑚𝑚 2𝑚𝑚𝑚𝑚
𝜓𝜓𝐼𝐼𝐼𝐼 𝑥𝑥 = 𝐴𝐴 sin 𝑥𝑥 + 𝐵𝐵 cos 𝑥𝑥
ℏ ℏ
• At 𝑥𝑥 = 0, the conditions for smooth joining require 𝜓𝜓
and 𝑑𝑑𝑑𝑑/𝑑𝑑𝑑𝑑 to match up (𝑘𝑘 = 2𝑚𝑚𝑚𝑚/ℏ) :
𝐶𝐶 = 𝐵𝐵 Continuity of 𝜓𝜓
𝐶𝐶𝐶𝐶 = 𝐴𝐴𝐴𝐴 Continuity of 𝑑𝑑𝜓𝜓/𝑑𝑑𝑑𝑑

150
 Wave Mechanics
• Dividing the second equation by the first eliminates 𝐶𝐶:
𝛼𝛼 𝐴𝐴
=
𝑘𝑘 𝐵𝐵
• Similarly, smooth joining at 𝑥𝑥 = 𝐿𝐿 requires:
Cont. of 𝜓𝜓
𝐴𝐴 sin 𝑘𝑘𝑘𝑘 + 𝐵𝐵 cos 𝑘𝑘𝑘𝑘 = 𝐺𝐺𝑒𝑒 −𝛼𝛼𝛼𝛼
𝑑𝑑𝜓𝜓
𝐴𝐴𝑘𝑘 cos 𝑘𝑘𝑘𝑘 − 𝐵𝐵𝑘𝑘 sin 𝑘𝑘𝑘𝑘 = −𝛼𝛼𝐺𝐺𝑒𝑒 −𝛼𝛼𝛼𝛼 Cont. of
𝑑𝑑𝑑𝑑

• Dividing the second equation by the first eliminates 𝐺𝐺.

• Replacing 𝐴𝐴/𝐵𝐵 with 𝛼𝛼/𝑘𝑘, we get:
𝛼𝛼/𝑘𝑘 cos 𝑘𝑘𝑘𝑘 − sin 𝑘𝑘𝑘𝑘 𝛼𝛼
=−
𝛼𝛼/𝑘𝑘 sin 𝑘𝑘𝑘𝑘 + cos 𝑘𝑘𝑘𝑘 𝑘𝑘

151
 Wave Mechanics
• For a specified well height 𝑈𝑈0 and width 𝐿𝐿, this
last relation can only be satisfied for special
values of 𝐸𝐸.
• For any other energies, the waveform will not
match smoothly at the well edges, leaving a wave
function that is physically inadmissible.
• Note that the equation cannot be solved explicitly
for 𝐸𝐸; rather, solutions must be obtained using
numerical or graphical methods.
152
 Wave Mechanics
• Energy Eigenvalues: Numerical solution of the problem
gives a series of increasing energy values.
• The number of energy values is finite rather than infinite,
because the energy cannot be allowed to exceed the value
of 𝑈𝑈0 .
• For example, for a well with 𝐿𝐿 = 0.1 nm and 𝑈𝑈0 = 400 eV,
we get ONLY FOUR possible energies:
𝐸𝐸1 = 26 eV,
𝐸𝐸2 = 104 eV,
𝐸𝐸3 = 227 eV,
𝐸𝐸4 = 375 eV
Note that the these are smaller than
those for an infinite well of same width:
38 eV, 150 eV, 338 eV, 602 eV 153
 Wave Mechanics
• E. The Square Potential Barrier:
• The square barrier is represented by a potential
energy function 𝑉𝑉(𝑥𝑥) that is constant at 𝑈𝑈0 in the
barrier region, say between 𝑥𝑥 = 0 and 𝑥𝑥 = 𝐿𝐿,
and zero outside this region:
𝑈𝑈0 for 0 ≤ 𝑥𝑥 ≤ 𝐿𝐿
𝑉𝑉 𝑥𝑥 = �
0 otherwise
• Particles with energy 𝐸𝐸 less
than 𝑈𝑈0 are incident from
the left.

154
 Wave Mechanics
• The wave function has three different forms in
the three regions 𝐼𝐼, 𝐼𝐼𝐼𝐼, 𝐼𝐼𝐼𝐼𝐼𝐼.
𝑼𝑼 = 𝑼𝑼𝟎𝟎
• Classically particles with
energy 𝐸𝐸 < 𝑈𝑈0 are turned
back (reflected) by the
barrier, having insufficient
energy to cross or penetrate it.
• Region 𝐼𝐼 is classically allowed while regions 𝐼𝐼𝐼𝐼
and 𝐼𝐼𝐼𝐼𝐼𝐼 are classically forbidden.

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 Wave Mechanics
• Region 𝑰𝑰: The wave function here is composed of the
two free particle plane waves:
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐴𝐴 𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘−𝜔𝜔𝜔𝜔) + 𝐵𝐵𝑒𝑒 −𝑖𝑖(𝑘𝑘𝑘𝑘+𝜔𝜔𝜔𝜔)
with 𝑘𝑘 = 2𝑚𝑚𝑚𝑚/ℏ2
• The first part corresponds
to the incident wave,
forward travelling while
the second part consists
of the reflected free-
particle wave.
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• Region 𝑰𝑰𝑰𝑰 : Classically, the particles should never
appear at 𝑥𝑥 > 𝐿𝐿, because they do not have sufficient
energy to overcome the barrier.
• However, quantum mechanically there is a finite
chance of the particles to be in region 𝑰𝑰𝑰𝑰.
• This situation is an example of barrier penetration,
sometimes called quantum mechanical tunneling.
• Particles can not be observed while they are in the
classically forbidden region 0 ≤ 𝑥𝑥 ≤ 𝐿𝐿 , but can
“tunnel” through that region and be observed at 𝑥𝑥 >
𝐿𝐿.

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 Wave Mechanics
• The Schrödinger equation for the region 𝐼𝐼𝐼𝐼 is:
ℏ2 𝜕𝜕 2
− 2
𝜓𝜓 𝑥𝑥, 𝑡𝑡 + 𝑈𝑈0 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐸𝐸𝐸𝐸(𝑥𝑥, 𝑡𝑡)
2𝑚𝑚 𝜕𝜕𝑥𝑥
• For time-independent potential, we have a variable
separable solution of the form:
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝜓𝜓 𝑥𝑥 𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖
• Thus we get the time-independent Schrödinger equation:
𝑑𝑑 2 𝜓𝜓 2𝑚𝑚 𝑈𝑈0 − 𝐸𝐸 2 𝜓𝜓(𝑥𝑥)
= 𝜓𝜓 𝑥𝑥 = 𝛼𝛼
𝑑𝑑𝑥𝑥 2 ℏ2
• With 𝐸𝐸 < 𝑈𝑈0 , we get 𝛼𝛼 = 2𝑚𝑚 𝑈𝑈0 − 𝐸𝐸 /ℏ2 as a real
number.

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 Wave Mechanics
• Hence we get:
𝑑𝑑 2 𝜓𝜓(𝑥𝑥)
− 𝛼𝛼 2 𝜓𝜓 𝑥𝑥 = 0
𝑑𝑑𝑥𝑥 2
• The complete wave function in the barrier is:
𝜓𝜓 𝑥𝑥 = 𝐶𝐶𝑒𝑒 −𝛼𝛼𝛼𝛼 + 𝐷𝐷𝑒𝑒 𝛼𝛼𝛼𝛼 for 0 ≤ 𝑥𝑥 ≤ 𝐿𝐿
• Region 𝑰𝑰𝑰𝑰𝑰𝑰: To the right of the barrier, where, again,
the particle is free and we get the wave function as:
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐹𝐹 𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘−𝜔𝜔𝜔𝜔) + 𝐺𝐺𝑒𝑒 −𝑖𝑖(𝑘𝑘𝑘𝑘+𝜔𝜔𝜔𝜔)
with 𝑘𝑘 = 2𝑚𝑚𝑚𝑚/ℏ2
• However, there should not be any backward going
wave in region 𝐼𝐼𝐼𝐼𝐼𝐼 which gives 𝐺𝐺 = 0.

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• Boundary Conditions:
• The coefficients 𝐶𝐶 and 𝐷𝐷 are fixed by requiring
smooth joining of the wave function across the
barrier edges:
• From the continuity of 𝜓𝜓 and 𝑑𝑑𝑑𝑑/𝑑𝑑𝑑𝑑 at the
boundaries at 𝑥𝑥 = 0 and 𝑥𝑥 = 𝐿𝐿:
𝐴𝐴 + 𝐵𝐵 = 𝐶𝐶 + 𝐷𝐷
𝑖𝑖𝑖𝑖𝑖𝑖 − 𝑖𝑖𝑖𝑖𝑖𝑖 = 𝛼𝛼𝛼𝛼 − 𝛼𝛼𝛼𝛼
𝐶𝐶𝑒𝑒 −𝛼𝛼𝛼𝛼 + 𝐷𝐷𝑒𝑒 +𝛼𝛼𝛼𝛼 = 𝐹𝐹𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖
𝛼𝛼𝛼𝛼 𝑒𝑒 +𝛼𝛼𝛼𝛼 − 𝛼𝛼𝛼𝛼 𝑒𝑒 −𝛼𝛼𝛼𝛼 = 𝑖𝑖𝑖𝑖𝑖𝑖𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖

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• Dividing through 𝐴𝐴 gives four equations in the fours
ratios 𝐵𝐵/𝐴𝐴, 𝐶𝐶/𝐴𝐴, 𝐷𝐷/𝐴𝐴 and 𝐹𝐹/𝐴𝐴.
• These can be solved by repeated substitution to find
𝐵𝐵/𝐴𝐴 in terms of the barrier height 𝑈𝑈0 , the barrier
width 𝐿𝐿, and the particle energy 𝐸𝐸.
• Reflection Coefficient 𝑹𝑹:
• The reflection coefficient 𝑅𝑅 for the barrier is the ratio
of the reflected probability density to the incident
probability density:
2 −𝑖𝑖 𝑘𝑘𝑘𝑘+𝜔𝜔𝜔𝜔 2 2
𝜓𝜓𝑅𝑅𝑅𝑅 𝐵𝐵𝑒𝑒 𝐵𝐵
𝑅𝑅 = 2
= 2 = 2
𝜓𝜓𝐼𝐼𝐼𝐼 𝐴𝐴 𝑒𝑒 𝑖𝑖 𝑘𝑘𝑘𝑘−𝜔𝜔𝜔𝜔 𝐴𝐴

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 Wave Mechanics
• In terms of wave theory, 𝑅𝑅 is the fraction of wave
intensity in the reflected beam.
• In terms of the particle picture, 𝑅𝑅 is the likelihood
(probability) that a particle incident on the barrier from
the left is reflected by it.
• Transmission Coefficient 𝑻𝑻:
• The transmission coefficient 𝑇𝑇 for the barrier is the
ratio of the transmitted probability density to the
incident probability density:
2 −𝑖𝑖 𝑘𝑘𝑘𝑘+𝜔𝜔𝜔𝜔 2 2
𝜓𝜓 𝑇𝑇𝑇𝑇 𝐹𝐹𝑒𝑒 𝐹𝐹
𝑇𝑇 = 2
= 2 = 2
𝜓𝜓𝐼𝐼𝐼𝐼 𝐴𝐴 𝑒𝑒 𝑖𝑖 𝑘𝑘𝑘𝑘−𝜔𝜔𝜔𝜔 𝐴𝐴

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 Wave Mechanics
• It is the relative intensity of this transmitted
wave.
• The transmission coefficient 𝑇𝑇 measures the
likelihood (probability) that a particle incident on
the barrier from the left penetrates to emerge on
the other side.
• Since a particle incident on the barrier is either
reflected or transmitted, the probabilities for
these events must sum to unity:
𝑅𝑅 + 𝑇𝑇 = 1
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 Wave Mechanics
• Further, the degree of transmission or
reflection will depend on particle energy.
• In the classical case, 𝑇𝑇 = 0 (and 𝑅𝑅 = 1) for
𝐸𝐸 < 𝑈𝑈0 , but 𝑇𝑇 = 1 (and 𝑅𝑅 = 0) for 𝐸𝐸 > 𝑈𝑈0 .
• The wave-mechanical predictions for the
functions 𝑇𝑇(𝐸𝐸) and 𝑅𝑅(𝐸𝐸) are much more
complicated.

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• Transmission Co-efficient 𝑻𝑻: A detailed solution
for the ratio 𝐵𝐵/𝐴𝐴 and hence the transmission co-
efficient is left as a problem.
• But we can use the results and the transmission
co-efficient is found to be:
2 −1
1 𝑈𝑈0
𝑇𝑇 𝐸𝐸 = 1 + sinh2 𝛼𝛼𝛼𝛼
4 𝐸𝐸 𝑈𝑈0 − 𝐸𝐸
• The equation is valid only for only for energies E
below the barrier height 𝑈𝑈0 .

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 Wave Mechanics
• A sketch of the transmission coefficient 𝑇𝑇 𝐸𝐸
for a square barrier is shown below:

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 Wave Mechanics
• Transmission Resonance: For 𝐸𝐸 > 𝑈𝑈0 , 𝛼𝛼
becomes imaginary and sinh(𝛼𝛼𝐿𝐿) turns
oscillatory.
• This leads to fluctuations in 𝑇𝑇(𝐸𝐸) and there are
isolated energies for which transmission occurs
with complete certainty, that is, 𝑇𝑇 𝐸𝐸 = 1.
• Such transmission resonances arise from wave-
interference and constitute further evidence for
the wave nature of matter.
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 Wave Mechanics
• Approximate Transmission Co-efficient:
• Approximation-1:For the potential barrier 𝑈𝑈0 high
relative to the energy 𝐸𝐸 of the incident particles,
we have:
𝛼𝛼 = 2𝑚𝑚 𝑈𝑈0 − 𝐸𝐸 /ℏ2 ≈ 2𝑚𝑚𝑈𝑈0 /ℏ
• Approximation-2: Let us also assume that the
barrier is wide enough for 𝜓𝜓𝐼𝐼𝐼𝐼 to be severely
weakened between 𝑥𝑥 = 0 and 𝑥𝑥 = 𝐿𝐿.
• This implies that: 𝑒𝑒 𝛼𝛼𝛼𝛼 ≫ 𝑒𝑒 −𝛼𝛼𝛼𝛼 which gives:
sinh2 𝛼𝛼𝛼𝛼 ≈ exp 2𝛼𝛼𝛼𝛼

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• Hence, we get the transmission co-efficient as:
2 −1
1 𝑈𝑈0
𝑇𝑇 𝐸𝐸 = 1 + sinh2 𝛼𝛼𝛼𝛼
4 𝐸𝐸 𝑈𝑈0 − 𝐸𝐸
−1
1 𝑈𝑈02
⇒ 𝑇𝑇 𝐸𝐸 ≈ 1 + exp 2𝛼𝛼𝛼𝛼
4 𝐸𝐸 𝑈𝑈0 − 𝐸𝐸
−1
1 𝑈𝑈0
⇒ 𝑇𝑇 𝐸𝐸 ≈ 1 + exp 2𝛼𝛼𝛼𝛼
4 𝐸𝐸
• Since we have assumed, 𝑈𝑈0 ≫ 𝐸𝐸, and also 𝛼𝛼𝛼𝛼
large, we can ignore the unity in the bracket.
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 Wave Mechanics
• Hence we get,
4𝐸𝐸
𝑇𝑇 𝐸𝐸 ≈ exp −2𝛼𝛼𝛼𝛼
𝑈𝑈0
• Again, to a reasonable approximation, we may take
4𝐸𝐸 ≈ 𝑈𝑈0 to get:
𝑇𝑇 𝐸𝐸 ≈ exp −2𝛼𝛼𝛼𝛼 = 𝑒𝑒 −2𝛼𝛼𝛼𝛼
• Example-12: Electrons with energies of 1.0 eV and 2.0 eV
are incident on a barrier 10.0 eV high and 0.50 nm wide.
• (a) Find their respective transmission probabilities. (b)
How are these affected if the barrier is doubled in width?

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• Solution-12: For the 1.0-eV electrons:
𝛼𝛼 = 2𝑚𝑚(𝑈𝑈0 − 𝐸𝐸)/ℏ
2 9.1 × 10−31 kg 10 − 1 eV
⇒ 𝛼𝛼 =
1.054 × 10−34 J.s
2 511keV/𝑐𝑐 2 9 × 10−3 keV
⇒ 𝛼𝛼 = = 1.6Å−1
1.973keV. Å/𝑐𝑐
• Since 𝐿𝐿 = 0.50 nm = 5.0Å, 2𝛼𝛼𝛼𝛼 = 16
• Hence the approximate transmission probability
is: 𝑇𝑇1 ≈ exp −2𝛼𝛼𝛼𝛼 = exp −16 ≈ 1.1 × 10−7
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• Solution-12 (contd.):Thus, one 1.0-eV electron out of
8.9 million can tunnel through the 10-eV barrier on the
average.
• For the 2.0-eV electrons a similar calculation gives:
𝑇𝑇2 ≈ 2.4 × 10−7
• Thus these electrons are approximately over twice as
likely to tunnel through the barrier.
• (b) If the barrier is doubled in width to 1.0 nm, the
transmission probabilities become:
𝑇𝑇1 ′ ≈ 1.3 × 10−14 , 𝑇𝑇2′ ≈ 5.1 × 10−14
• Evidently T is more sensitive to the width of the barrier
than to the particle energy here.
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