Notes on PSO201A (Quantum Physics; 2019-20-II)

Anjan K. Gupta, Department of Physics, IIT Kanpur

1 The beginning of QM
I like to start this course with a remark by the famous Nobel laureate physicist Albert
Michelson (or Michelson-Morley experiment) to an audience in 1894. He said, “It seems
probable that most of the ground underlying principles have been firmly established and that
further advances are to be sought chiefly in the rigorous applications of these principles
to all phenomena which come under our notice..... The future truths of physics are to be
looked for in the sixth place of decimals.”
This was a very inappropriate time for this statement as in 1894 itself Becquerel dis-
covered radioactivity followed by X-rays discovery by Röntzen in 1896. In 1897, Thomson
discovered electrons, which changed the course of developments with the immediate ques-
tion like how a neutral atom could form. The plum pudding model of Thomson was
proved wrong by Rutherford by scattering α-particles from gold foils leading to a nuclear
model with the electrons bound to a positive nucleus by Coulomb force and orbiting like
planets around Sun. But this was problematic as an accelerating charge particle radiates
which raised questions about stability of an atom. Bohr proposed a model that could
explain the spectral lines of hydrogen. Some of these excitements can be lived through
by reading a first 5 chapters of a book, ”Second Creation” by Crease and Mann. One can
easily google to find the chronology of the early developments in quantum mechanics that
began in the last decade of 19th century.
The experiments and theories that eventually led to various aspects of quantum me-
chanics can be broadly divided into two categories, namely ”particle nature of waves”
and ”wave nature of particles”. We review some of the experiments below to inspire an
unease on wave-particle duality.

1.1 Particle nature of waves

There are several experimental results that could only be explained when one incorporated
a particle nature of waves in the sense that one can exchange energy (and momentum)
with these waves in a quantum of certain amount or these waves exhibit energy as integer
number of such quanta. These experiments include, 1) Black body radiation, 2) Photo-
electric effect, 3) certain aspects of X-rays, 4) Heat capacity of solids, 5) light detection
as quanta of energy and single photon interference. Below we discuss these experiments
and how they get explained by the particle or quantum nature of waves.

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1.1.1 Black body radiation
Heated objects emit black body radiation with a characteristic spectrum determined by
temperature. A black body is an object that absorbs all the em-radiation falling on it.
This is an idealization of practical situations and such ideal Black body spectrum can
be theoretically explained. The spectrum is defined by I(λ)dλ which represents the em-
energy emitted in wavelength window λ to λ+dλ or by ρ(ν)dν which is the energy emitted
in frequency range ν to ν + dν.
A blackbody can be constructed by using a highly absorbing (non-transmitting) walls.
Further, one can geometry confine all em-radiation by collecting all the scattered light from
walls to within the cavity. One possible construction is as shown. This is an idealization
and in reality if the cavity is made of a particular material with a characteristic emission
spectrum, the radiation inside will not have typical blackbody characteristics. We, here,
are not concerned with such non-ideal situations.

Figure 1: The blackbody spectrum, i.e. energy density Vs λ, at two different temperatures.
The peak wavelengths are marked by λm1 and λm2

Blackbody spectrum has been measured in laboratories. When Planck worked on

his theory several experimental data were available and they showed disagreement with
existing theories. Before Planck’s theory, the blackbody spectrum, as shown, was known
to have certain characteristic features. A maximum at a particular wavelength λm that
depended on temperature as given by

λm T = 2.898 × 10−3 m-K. (1)

This is known as Wien’s displacement law. For Sun λm = 5100 Å leading to T = 5900◦ C.
In fact Wien had already argued about the general features of the blackbody spectrum
using thermodynamics arguments. Another known law, again from thermodynamics ar-
guments, was Stefan-Boltzmann law of radiation, i.e. the power emitted by a black body
per unit surface area is given by

u = σT 4 (2)

with σ = 5.67 × 10−8 W/m2 -K4 . Also, before Planck two attempts were made to un-
derstand blackbody spectrum which were only partially successful. One was a theory by
Rayleigh-Jeans and another by Wien.
With this as background let us discuss how we understand the blackbody radiation
now. In order to find the energy density due to em-waves inside a cavity in thermal

2
equilibrium at temperature T we need to find two things: 1) Number of em-modes in
frequency range ν to dν, i.e N (ν)dν and 2) Energy contained in each mode per unit
volume at temperature T . The net energy per unit volume in frequency range ν to dν
will be the product of the two, i.e.

ρ(ν)dν = N (ν)dν × (average energy in each mode at temperature T) (3)

So our first task is to find N (ν)dν. For this we consider stationary em-waves in a cube
shaped cavity. It turns out that the mode density is actually independent of the exact
shape for macroscopic objects.

Figure 2: Left: The stationary modes of a 1D cavity of length L in real space. Right:
The discrete allowed mode in k-space

Before analyzing a three-dimensional cubic cavity let’s first discuss the plane stationary
waves in a one dimension confined between x = 0 and L. The waves will exhibit nodes at
the two ends and thus the wavelength of permitted modes will be given by λn = 2L/n,
see figure. Thus the associated wave-number is given by kn = 2π/λn = nπ/L. Hence
the separation between the wave-numbers of the neighboring modes ∆k = π/L. We also
have νn λn = c and so νn = ckn /2π and ∆ν = cπ/2L. Since L is a large length scale and
so these modes will be extremely close to each other. Thus number of modes in a small
dk-interval will be given by 2 × dk/(π/L). The factor of two here is due to two different
polarizations of em-wave. In 2D one gets kx = nx π/L and ky = ny π/L with nx , ny as
positive non-zero integers. If we look at the modes in a 2D square shaped cavity kx , ky
plane we get a square-grid of discrete points with separation ∆kx = ∆ky = π/L. The
number of modes between k and k + dk can be found by finding the number of discrete
points in one-quarter of a circular shell of radius k and thickness dk. This shell will have
an area 2πkdk/4. Each discrete point in 2D k-space occupies an effective area (π/L)2 ,
giving number of discrete points as (πkdk/2)/(π/L)2 .
In 3D cubic cavity, one gets kx = nx π/L, ky = ny π/L and kz = nz π/L giving a
3D grid of points in 3D k-space with each point effectively occupying a volume (π/L)3 .
−
→ p
For a given point the magnitude of wave-vector would be | k | = kx2 + ky2 + kz2 which
determines the overall frequency and wavelength of this particular mode. To find the
number of total modes in an a volume of k-space between k and k = k + dk, this volume
is given by one octant of a spherical shell of radius k and thickness dk, i.e. 4πk 2 dk/8.
With the volume of each discreet k-point as (π/L)3 , we get the number discreet k-points as
(πk 2 dk/2)/(π/L)3 = L3 k 2 dk/2π 2 . Now counting the independent polarization that each
discrete k-point exhibits we get to number of modes per unit volume as N (k)dk = k 2 dk/π 2 .

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Figure 3: The discrete allowed mode in k-space for a 2D square cavity of side L. The ring
like region of width dk and radius k encompasses good number of such discrete points
that can be found from (2πkdk/4)/(π/L)2 .

By using ν = ck/2π we get dk = (2π/c)dν N (ν)dν = (2π/c)3 ν 2 dν/2π = 8πν 2 dν/c3 .

Similarly in terms of λ we get N (λ)dλ = (8π/λ4 )dλ.
Rayleigh-Jeans law: Now our task is to find the average energy contained in thermal
equilibrium at temperature T in each mode. This is where there is a discrepancy between
classical average energy per mode expression with quantum one. The classical black body
radiation was derived by Rayleigh-Jeans where one uses equipartition theorem to find the
average energy contained in each mode. According to classical mechanics the energy in
each mode will be proportional to the square of the amplitude of electric field of that mode,
i.e. Energy = αE02 . The relative probability of E0 taking this particular value is given
by the Boltzmannn factor, i.e. exp(−Energy/kB T ). Thus we see that the probability of
occupancy reduces exponentially with energy. Since classically E0 can take any arbitrary
positive value (for the stationary mode) the average energy per mode will be given by
R∞
0R
αE02 exp(−αE02 /kB T )dE0
∞ (4)
0
exp(−αE02 /kB T )dE0
which works out as R ∞kB T /2, i.e. independent
p of α.R The mathematics here requires
p two
∞
integrals, namely 0 exp(−βx2 )dx = π/4β and 0 x2 exp(−βx2 )dx = (1/2β) π/4β.
The second integral can be obtained by differentiating the first one wrt β.
This is the reasoning behind the so called equipartition theorem where if the energy
with respect to a continuous system variable x is quadratic in x then the average energy at
temperature T associated with x degree of freedom is kB T /2. This is what one uses when
writing the total energy associated with a monatomic ideal gas as 3kB T /2 per atom which
comes from the three components of the momentum vector. For em-wave mode there is
also the energy associated with the magnetic field B0 which is again quadratic with B0 .
Thus we get total energy per mode as kB T . This leads to the energy per unit volume in
the black body cavity from ν to ν + dν as ρ(ν)dν = (8πν 2 /c3 )kB T dν. This is called the
classical Raylegh Jeans law. Although there is fair agreement between Rayleigh-Jeans
law and experiments for small ν values, there are several problems: 1) ρ(ν) diverges with
ν as opposed to experiments which show a peak with an exponential decline at large ν.
2) The total energy density, obtained by integrating ρ(ν) over ν = 0 to ∞, diverges.
Wien’s law Wien argued from thermodynamic arguments [see M.K. Harbola, “The
genesis of quanta”, Resonance, Feb 2008, p.134] that ρ(ν) must have a form like ν 3 ϕ(ν/T )

4
where ϕ(x) is some unknown function of x. In fact people thinking of alternate theories
to classical thermodynamics believed in Boltzmann theory very strongly and they did
not want to sacrifice it. Wien further argued that the frequency of emitted em-radiation
from molecules must be proportional to their kinetic energy, i.e. mv 2 /2 = aν and so the
intensity of radiation should be proportional to the number of molecules at that kinetic
energy, i.e. exp(−aν/kB T ). Thus he proposed ρ(ν) = (Aν 3 /c4 ) exp(−bν/kB T ) with A, b, c
as constants. Or one can also write ρ(ν) = (A/λ5 ) exp(−b/λT ). This function shows a
maxima at some λm as seen in experiments. On maximizing this leads leads to λm T = b/5.
This gave a reasonable agreement with the experiments with Wien’s constant b found from
experiments. Wien got Nobel prize in 1911 for his contribution to the understanding of
the black body radiation.
Planck’s theory of black body radiation: Planck proposed that em-radiation
comes in quanta and the E and B fields cannot take arbitrary values. It turns out that
the quantum theory of em-radiation is much more complex and it came much later as
quantum electrodynamics (QED) which quantized the em-fields. This is way beyond the
scope of this course.
Planck argued that for a given frequency-ν mode the energy can take values 0, hν, 2hν,
3hν, ...., i.e. nhν. The relative probability to have one quantum of energy is exp(−hν/kT )
and for two quanta it is exp(−2hν/kT ) and for n-quanta it is exp(−nhν/kT ). So total
energy associated with a frequency ν mode will be
P∞
(nhν) exp(−nhν/kT )
P∞
n=0
(5)
n=0 exp(−nhν/kT )
P
. The series’ inPthe numerator and denominator can be easily summed using ∞ n
n=0 x =
∞
1/(1 − x) and n=0 nx = x/(1 − x) . The first is a geometric series and the second one
n 2

can be obtained by differentiating the first result wrt x. Here x = exp(−hν/kT ). Thus
the final average energy in ν-frequency mode works out as hν/[exp(hν/kT ) − 1]. This
leads to the Planck’s law of black body radiation as:
8πhν 3 1
ρ(ν)dν = dν. (6)
c exp(hν/kT ) − 1
3

This also leads to

8πhc 1
ρ(λ)dλ = dλ. (7)
λ exp(hc/λkT ) − 1
5

One can easily see that in the limit of large frequencies, i.e. hν ≫ kB T one gets the
Wien’s law from Planck’s expression and in the opposite limit hν ≪ kB T , it agrees with
Rayleigh-Jeans law. Also one gets the precise Wien’s displacement law from Planck’s
expression (homework) as hc/λm kB T = 4.967. From the then known Wien’s constant
one could easily find the value of h/kB . Another known law at that time was Stefan’s
law i.e., energy radiated from a black body surface per unit area and per unit time is
σT 4 with experimentally known σ value of 5.67×10−8 Wm−2 K−4 . The Stefan’s law can
be easily derived from Planck’s law giving σ = 2π 5 kB
4
/15c2 h3 . This helped Planck deduce
h = 6.55 × 10−34 J-s and kB = 1.346 × 10−23 J/K. This did not help much as none of these
were known independently by any other method. But the gas constant R was known

5
which helped Planck deduce Avogadro number NA = R/kB as 6.175×102 3 per mole. Also
Faraday constant, i.e. charge in one mole of singly charged ions, F was known so Planck
could find e = F/NA . This prediction was shortly confirmed by Geiger and Rutherford
by finding charge on α-particles. The agreement between the two was within about 1%.

1.1.2 photoelectric effect

This experiment used a simple setup as shown in figure with two electrodes inside an
evacuated glass bulb. The light falling on one electrode leads to photo-induced electrons’
emission with certain kinetic energies. The applied voltage prohibits electron below certain
kinetic energy from reaching the other electrode and thus the current reduces as the
voltage is increased and beyond a threshold voltage Vth the current becomes zero. It was
experimentally found that: 1) The current (I) depended on light intensity, wavelength
both as well as on applied voltage, 2) For fixed wavelength λ, there is a threshold voltage
Vth above which there is no current. The general behaviour of current is depicted in figure.
The threshold voltage was found to vary with λ but not with the light intensity.

Figure 4: Photo-electric effect.

The explanation for this behaviour was given by Einstein in 1905 for which he got
Nobel prize. Einstein proposed that the electrons absorb only a quantum of energy from
incident light given by hν and come out of the metal as free electrons with kinetic energy
T = hν − ϕ where ϕ is the work function energy barrier which protects the electrons
from coming out of the metal. The metal has a continuous distribution of electrons below
certain energy, called Fermi energy EF , which is energy ϕ below the vacuum energy. Thus
one gets electrons with kinetic energy ranging from zero (i.e. for electrons excited from
hν − ϕ below EF ) and up to kinetic energy hν − ϕ (i.e. for electrons excited right from
EF ). As a result with increasing V less electrons will make it to the other electrode
and above eVth = hν − ϕ, no electron will make it to the second electrode. Thus we get,
Vth = (h/e)ν −ϕ/e. This linear relation between Vth and ν was found to be experimentally
correct with its slope well described by h/e. This could also help in deducing the work
function of the metal. The critical part of the argument was the absorption of light
happens only in one quantum hν of energy from light wave indicating the quantization of
energy associated with light wave.
Another interesting consequence of this experiment is the technique of ”photo-electron
spectroscopy” which helps us probe the number of electronic states available in a conductor
at different energies below the Fermi energy. This has been a very successful probe as it

6
 Figure 5: Photoemission spectroscopy.

has helped us understand the physics of the electrons in many solids. In the modern photo-
electron spectroscopy experiments one uses highly monochromatic light (from Lasers or
more sophisticated sources) with very sophisticated electron energy analyzers. This helps
one deduce the distribution of electronic states in solids with great energy resolution. In
fact, one can also get momentum information of the electron with detectors capable of
fine angular resolution.

1.1.3 X-rays
X-rays were discovered by Röntzen in 1895 by a process called Bremstrahlung, i.e. sudden
deceleration of electrons in a metal leadin to em-radiation. This is actually an inverse pho-
toelectric effect as high-energy electrons impinging on a metal electrode lead to emission
of X-rays. The X-ray emission is related to atomic transitions. There is one interesting
fact that had consequences for the development of quantum mechanics. This was about
the detailed distribution of X-ray intensity as a function of wavelength, λ. It was found
that emitted X-ray intensity vanished below certain wavelength λth . Further, this λth
was dependent on the kinetic energy of the impinging electrons or rather the voltage V
through which the electrons were accelerated before striking the metal electrode. Thus
λth was found to depend on V as,

12.4Å
λth = . (8)
V (in kV)

Figure 6: X-rays generation and characteristics.

This behavior can be readily understood as the maximum energy that an X-ray photon
can carry will be limited by the electron’s kinetic energy. The photon energy can always be

7
less as the electron can loose energy to other non-radiative processes. Thus the maximum
photon energy hc/λth = eV or
hc 6.6 × 10−34 × 3 × 108 12.4 × 10−10 12.4
λth = = m = m= Å. (9)
eV 1.6 × 10 −19 × V (in kV) × 103 V (in kV) V (in kV)
This agress with experiments nicely. X-rays have any applications. The two noteworthy
are in medical diagnostics and in finding the crystal structure analysis. In fact the above
relation is useful to remember as a conversion formula between energy (in keV) and
wavelength (in Å).

1.1.4 Compton scattering

This experiment is about the scattering of X-rays by free electrons in a metal which
initially have negligible kinetic energy. This effect brought more particle-like aspects of
light as one needs to use quantized energy as well as momentum of a photon in order to
understand Compton scattering. The energy exchange between X-ray photon and electron
is large for Compton scattering to be observable taking the electron into relativistic regime.
Thus one needs to use the relativistic energy momentum relation for electron, i.e. E 2 =
p2 c2 + m20 c4 . Here E is the total energy, including the rest mass energy m0 c2 , and p is
the momentum. For photon the energy is given by hν = hc/λ while its momentum is
hν/c = h/λ.

Figure 7: The left schematic shows the X-ray photon and electron before scattering,
the middle one shows them after scattering. The right schematic is the experimental
setup showing the incident X-ray beam and the Compton scattered beam analyzed by the
detector at scattering angle θ.

One needs to write the energy and momentum conservation for a 2D scattering problem
as shown in figure. For electron initially at rest, the energy conservation gives:
q
hν + m0 c = p2 c2 + m20 c4 + hν ′
2
(10)

The momentum conservation along the direction of initial photon momentum gives
h h
= ′ cos θ + p cos ϕ. (11)
λ λ
The momentum conservation in the direction perpendicular to the initial photon momen-
tum gives
h
0=− sin θ + p sin ϕ. (12)
λ′

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We thus get only three equations but there are four unknowns, namely p, ϕ, λ′ and θ.
We can eliminate two unknowns and find a relation between the remaining two. This
is dictated by experimental setup where one measured the scattered X-ray spectrum at
different scattering angles. Thus we eliminate the electron variables p and ϕ to find a
relation between λ′ and θ. From last two equations, we get
 2
h2 h h
p cos ϕ + p sin ϕ = ′2 sin θ + − ′ cos θ + −
2 2 2 2 2
λ λ λ
2 2 2
h h 2h
or p2 = ′2 + 2 − ′ cos θ
λ λ λλ
or p c =h ν + h ν − 2h2 νν ′ cos θ after using λ = c/ν.
2 2 2 2 2 ′2

Using the last relation in the first equation, we get

h2 ν 2 + h2 ν ′2 − 2h2 νν ′ cos θ + m20 c4 =(hν − hν ′ + m0 c2 )2

or − 2h2 νν ′ cos θ = − 2h2 νν ′ − 2hν ′ m0 c2 + 2hνm0 c2
 
m0 c2 1 1
or cos θ =1 + − (13)
h ν ν′
h
or λ′ − λ = (1 − cos θ) =λC (1 − cos θ). (14)
m0 c

Here λC = h/m0 c is called the Compton wavelength of electron whose value is 0.024Å.
Thus we see that the change in wavelength of the X-rays is rather small. In order to
resolve this change beyond the linewidth of the used X-rays one has to use X-rays of very
small wavelength or high energy. In actual experiment the X-ray beam strikes a metal foil
having free electrons as well as atoms. One measures the X-ray spectrum, i.e. intensity as
function of wavelength, at different scattering angle θ values. One sees two well separated
peaks in a typical spectrum, one elastic (i.e. at λ) and the other inelastic, at λ′ as
dictated by Compton formula. The elastic peak arises from the Compton scattering from
atoms which are much heavier than electrons and thus lead to a much smaller Compton
wavelength and thus there is negligible shift in λ of the X-rays that Compton scatter from
atoms.

Figure 8: The measured X-ray intensity as a function of wavelength at different scattering

angle θ values.

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1.2 Specific-heat of solids due to lattice
Solids get contribution to their specific heat from many internal degrees of freedom includ-
ing lattice vibrations and electrons (in metals). For insulators the specific heat is dictated
primarily by lattice contribution which we discuss here as it also played some role in the
development of quantum mechanics. There was certain understanding of the specific heat
which was derived from the classical equipartition theorem. For a solid containing N
atoms in a 3 dimensional solid there are 6 bulk degrees of freedom (dof ) that lead to bulk
translational and rotational kinetic energies arising from three linear momenta and three
angular momenta. The remaining 3N − 6 dof go in dictating these many lattice vibration
modes. An example in 3D would be taking a triangular molecule with three atoms at its
corner. It’ll exhibit 3 independent vibration modes.
Each vibration mode will have two forms of energy associated with it, namely kinetic
energy associated with the mode-momentum (p) and elastic potential energy associated
with the mode-displacement (x) as is the case with a single oscillator of fixed frequency.
The energy would be quadratic wrt both i.e. E = p2 /2m + kx2 /2. Thus from classical
equipartition theorem one get kB T /2 from x and p dof associated with each mode leading
to per mode average energy at temperature T as kB T . This leads to an average total
energy ⟨U ⟩ = (3N − 6)kB T and thus the molar specific heat as c = ∂⟨U ⟩/∂T = 3NA kB =
3R. Here R is the gas constant. This temperature independent classical expectation
is known as Dulong-Petit law. But this does not agree with experiments as the low
temperature specific heat of insulating solids is much smaller that 3R and it vanishes as
T → 0. Einstein proposed a quantum theory asserting that the lattice vibration energy
is actually quantized. Thus a frequency-ν vibration mode will take energy in quanta of
hν just like photons. In fact these a quantum of lattice vibration energy is analogously
called phonon. This is indeed the case as we shall see from the discussion of quantum
simple harmonic oscillator. Thus the relative probability of a mode exhibiting energy nhν
would be exp (−nhν/kB T ) and eventually just like the blackbody radiation discussion the
average energy associated with a mode at temperature T is given by
P∞
n=0 nhν exp (−nhν/kB T ) hν
⟨u⟩ = P ∞ = (15)
n=0 exp (−nhν/kB T ) exp (hν/kB T ) − 1

Figure 9: Temperature dependent specific heat of lattice.

Einstein assumed all the 3N − 6 lattice modes to be of same frequency ν and thus the
total energy of all the modes will be (3N − 6)⟨u⟩ and so the molar specific-heat of the

10
solid will be given by (ignoring 6 relative to NA ),
 
∂⟨u⟩ −3NA hν exp (hν/kB T ) hν
c =3NA = −
∂T [exp (hν/kB T ) − 1]2 kB T 2
 2
hν exp (hν/kB T )
or c =3R
kB T [exp (hν/kB T ) − 1]2
 2
TE exp (TE /T )
or c =3R . (16)
T [exp (TE /T ) − 1]2
Here TE = hν/kB is a material dependent fitting parameter called Einstein temperature.
We can easily check the result in the high and low temperature limits. This showed a
much better agreement with the experiments. For T ≫ TE , one gets c = 3R, consistent
with classical Dulong-Petit law. For T ≪ TE one gets c = 3R(TE /T )2 exp (−TE /T ). So c
does approach zero as T → 0. However the exp (−TE /T ) dependence is not what one sees
at low temperatures experimentally. One rather finds that c ∝ T 3 at low temperature.
Debye gave a more satisfactory theory incorporating the fact that all modes do not have
same frequency but rather one gets a systematic frequency dependent density of modes
from the dispersion of lattice vibrations in real solids.

1.2.1 Frank-Hertz experiment

Figure 10: Frank-hertz experiment schematic and voltage dependent plate current.

This experiment done in 1914 demonstrated that internal energy of an atom are quan-
tized in a way that the atoms can loose energy in inelastic collisions only in certain
quantum of energy. A vacuum triode-tube with three electrodes, namely cathode, grid
and plate was used as shown in figure. In evacuated tube the plate current rises mono-
tonically as a function of voltage V between cathode and grid. This happens as more
electrons that are emitted by heated cathode reach the plate when V is increased. Now
when the tube contained mercury vapor which is achieved by heating the tube to near
170◦ C to evaporate mercury sealed in the tube. The electrons that accelerate collide
with mercury atoms and loose some of the energy. It was found that the plate current
showed a non-monotonous behavior with V . In fact it showed a periodic pattern with
4.9 V period together with a rising background as shown in figure. This was interpreted
using the excitation energy of mercury atom as 4.9 eV and thus electrons loose energy

11
in collisions with mercury atoms only in multiple of 4.9 eV. A given electron can loose
energy to multiple Hg atoms within the limit of its total kinetic energy.

1.2.2 Single photon interference

This is a rather modern experiment using the Young’s double-slit interference setup but
with very faint light source and very sensitive light detector so as to detect photons one
by one. What one sees here is the same pattern but in discrete photon counts. So one sees
that the rate at which the photons arrive at the screen at a particular position matches
with the expected interference pattern. This leads to a particle like picture of photon but
with wave-like properties. There are some questions which are useful to ponder over from
this experiments. For example, what is the interference between?, two different photons?,
of a photon with itself?, of the different paths that a given photon can take? These
eventually lead to better insights into quantum mechanics.

1.3 Wave nature of particles and de Broglie hypothesis

Louis de Broglie proposed in 1923 in his Ph.D. thesis that matter particles actually behave
as waves. EM-waves or photons have a dual nature with photons having momentum
p = h/λ and energy E = hν as proved from the Compton effect experiments. The matter
particles also have a wave-like character with p = h/λ and E = hν or we can also write
p = ℏk and E = ℏω. Here ℏ = h/2π, k = 2π/λ √ and ω = 2πν. For eg., for an electron
with kinetic energy E = 1 keV we get λ = h/ 2mE = 0.38Å and ν = 2.4 × 10 7 Hz. For
1

matter objects with large mass, λ is very small so these objects follow laws of classical
physics. Even for electrons λ is quite small so one has to look for proper experiments to
verify its wave nature.

1.3.1 Davisson and Germer and Thomson experiment: electron interference

X-rays with their wavelength in 1Å were used by Bragg and others in 1912-13 to probe
the crystal structure of solids. Elasser suggested in 1926 that solids provide a periodic
lattice with periodicity that can be appropriate for probing wave nature of electrons.
Davisson and Germer conducted the first experiment in 1927 where they scattered an
electron beam from a nickel target and found that a peak in scattered electron intensity
occurs at a particular angle (ϕ = 50◦ ) for a particular energy of electron beam (54 eV).
This is shown in the polar plots together with experimental geometry in the figure. They
analyzed this using the interplanar distance in Ni as d = 0.91Å and the Bragg’s formula
2d sin θ = nλ with n = 1 and θ = 90 − (ϕ/2) as found by comparing the Bragg geometry
with experiment. As a result they found λ = 1.65Å which matched well with the de
Broglie wavelength of 1.65Å for 54 eV kinetic energy.
Thomson carried out similar experiment in a powder-diffraction geometry on powdered
Ni and found that the electrons making scattering rings on a screen kept in front of the
sample and perpendicular to the incident electron beam. A good agreement with de
Broglie hypothesis was thus found.
In modern times people have been able to do other diffraction and double slit inter-
ference with electrons and even atoms. In fact there are many applications of electron

12
 Figure 11: Davisson-Germer experiment.

Figure 12: Thomson experiment.

beams that exist precisely because of their wave nature. For instance scanning electron
microscope (SEM) gets a resolution in sub-nanometer range precisely because one can get
electron beams with sub-Å de Broglie wavelength and thus the diffraction limit leads to a
sub-Å resolution. In fact the eventual resolution limit in SEM comes from other consid-
erations including the energy spread and inter-electron interaction in the electron beam.
The transmission electron microscope (TEM) is another important tool that utilizes wave
nature of electrons to image solids with atomic resolution. Two important surface probes
are low energy electron diffraction (LEED) and reflecting high energy electron diffraction
(RHEED) which are used to monitor and track the atomic structure of the surface of the
thin films during film growth/deposition.

2 Formulation of quantum mechanics

From the experiments described above and de Broglie’s hypothesis we see: 1) energy
possessed by various atomic, sub-atomic objects and atomic lattice vibrations is quantized,
2) The em-waves behave as particle and wave both, and 3) the particles also behave
as waves. The last fact prompts one to the peculiar properties of waves that are also
possessed by particles. This leads to some very counter-intuitive phenomena and one of
this is uncertainty principle.

13
2.1 Heisenberg’s uncertainty principle
On the basis of wave-particle duality and de Broglie hypothesis Heisenberg proposed that
the uncertainty in a given particle’s position and momentum are inversely related. More
specifically he stated ∆p.∆x ≥ ℏ/2. We start this discussion by considering a wave,
y(x, t) = A sin(kx − ωt) with k = 2π/λ and ω = 2πν. As defined this wave exists
over whole space and, at all times. Now to get a space-localized wave or disturbance
one actually has to superpose waves of different λ values. These interfere to give a
rather localized entity that can describe a particle-like object. To get a feel of this let’s
superpose two waves of slightly different k. So we have y1 (x, t) = A sin(k1 x − ω1 t) and
y2 (x, t) = A sin(k2 x − ω2 t) and

y(x, t) =y1 (x, t) + y2 (x, t) = A sin(k1 x − ω1 t) + A sin(k2 xω2 t)

=2A sin[(k1 + k2 )x/2 − (ω1 + ω2 )t/2] cos[(k1 − k2 )x/2 − (ω1 − ω2 )t/2] (17)

. On simplifying, y(x) = 2A sin[(k1 +k2 )x/2−(ω1 +ω2 )t/2] cos[(k1 −k2 )x/2−(ω1 −ω2 )t/2].
This at a fixed time, say t = 0 shows a beat-like pattern if one plots it as a function of
x as shown in figure below. The width of each wave-group ∆x will be given by ∆x =
2π/(k1 − k2 ). The wave is made up of two different waves with k-values as k1 and k2
and thus one can see that the spread in k value is ∆ ∼ |k1 − k2 |. Using de Broglie’s
hypothesis, the spread in momentum is ∆p = ℏ|k1 − k2 |. Thus we get product of the
spread (or uncertainty) in x and p space as ∆px = [2π/(k1 − k2 )] × ℏ|k1 − k2 | = 2πℏ = h.

Figure 13: The top and middle show two waves with slightly different wavelengths and
the lower panel shows there superposition exhibiting beats-like pattern in real space.

In above illustration the beats-pattern still fills up the whole space and in order to
really get a space-confined wave one needs to superpose more k-waves. This is better
illustrated if we use the Fourier transforms to superpose many waves over a range of
k. For example if we superpose waves with different k complex waves, exp(ikx), such

14
Rthat the amplitude of the k-component is g(k) we’ll get a real space wave as y(x) =
g(k) exp(ikx)dk. This is actually the inverse Fourier transform of g(k). For instance,
if we choose g(k) = exp(−|k|/k0 ) which in k-space has a width ∆k ∼ k0 , we get y(x) ∼
[x2 +k0−2 ]−1 . This is a Lorenzian of width ∆x ∼ k0−1 . Thus we get the uncertainty product
∆p.∆x ∼ ℏ. Thus we see the connection of this uncertainty principle with the spread of
a complex function in x-space and p-space. This seems natural once we associate p with
λ as one needs many different λ or k-waves in order to create a localized wave that to
describe a particle.

2.2 group velocity

Another aspect of this wave superposition in order to get a localized wave, which I now
call a wave-packet, is the concept of group velocity as opposed to the phase velocity. For a
given wave dispersion relation, i.e. ω(k) the phase velocity is vp = ω(k)/k while the group
velocity is vg = dω/dk. The reason why this is relevant is because the wave-packet actually
moves with group velocity which for the matter waves is different from the phase-velocity.
To get a feel of group velocity we revisit the two-wave superposition, i.e. Eq. 17, which
led to the beat-like pattern. The phase velocity associated with the second cos-term,
which is responsible for the beat-like behavior, is actually (ω1 − ω2 )/(k1 − k2 ). This is
clearly different from the phase velocity vp = ω/k. In fact for the waves following certain
dispersion relation ω(k) the group velocity is given by vg = dω/dk. In fact the group
velocity can have a sign opposite to that of phase velocity. This was clearly illustrated in
the lecture using Mathematica simulations.

2.3 Experimental illustration of uncertainty principle

Above we discussed a somewhat mathematical approach to uncertainty principle based on
construction of a localized particle-like entity made up of different wavelength waves. We
now discuss two experimental illustrations of uncertainty principle. The rigorous mathe-
matical justification of both of these will eventually follow after using Fourier transforms.
In fact Heisenberg arrived at this hypothesis from the analysis of one such experiment.
Diffraction experiment: When one tries to localize a matter-wave in real space, it
inevitably leads to a spread or uncertainty in momentum. This attempt to localize is made
by putting a small slit of width ∆x = d in the path of a plane wave. In this case the wave
undergoes diffraction resulting into a spread in the x-component of its momentum. From
the width of the central maximum in the diffraction pattern on the screen kept far away
one can find that the angular spread (from −θ0 to +θ0 ) of the central maximum is given by
d sin θ0 = λ with λ as the wavelength of the plane wave. This amounts to a momentum
spread ∆px = (h/λ) sin θ0 . Thus the uncertainty product ∆px .∆x = (h/λ) sin θ0 × d.
Using d sin θ0 = λ we get ∆px .∆x = h. So we see that reducing ∆x leads to an increase
in ∆px as expected from uncertainty relation.
Microscope: Let’s try to measure a particle’s position by using a an optical mi-
croscope where one shines light on the particle and part of the light scattered from the
particle is directed towards the objective lens of a simple microscope. We use light of
wavelength λ. Since we detect photons in an angular spread given by the size of the lens
this will result into a momentum uncertainty (or spread) in px of the detected photons

15
Figure 14: The left schematic shows the diffraction of a plane wave when one tries to
constrain it using a slit. The right figure shows the objective lens of an optical microscope
which focuses the photons scattered from a particle in order to measure the particle’s
position.

given by ∆px = (h/λ) sin θ. This means that that the photons that we detect would
cause this much uncertainty in particle’s momentum. The lens has a diffraction limited
resolution of λ/ sin θ. So the particle will be detected with a minimum position uncer-
tainty of ∆x = λ/ sin θ. Thus we get the uncertainty product as ∆px .∆x = h. This
means that an effort to measure the position of a particle with precision ∆x will lead
to an uncertainty in its momentum of order h/∆x. This experiment makes the result
appear as an experimental limitation. However the analysis points towards an inherent
limitation. Measurements complicate and may be shadow this inherent nature which is
actually arising from the wave nature of particles.

2.4 Complementarity principle

The uncertainty principle is actually more prevalent and applies to many complementary
quantities, variables or observables. Some variables that complement each other to make
up a classical description are actually mutually exclusive. Some such complementary
variables are:
1) position (x) and momentum (px ): ∆x.∆px ≥ ℏ/2,
2) Energy (E) and time (t): ∆E.∆t ≥ ℏ/2,
3) Angular momentum (L) and angle (θ): ∆L.∆t ≥ ℏ/2.
We’ll discuss the time-energy uncertainty later. In above relations the formal definition
of uncertainty in variable z is ∆z 2 = ⟨z 2 ⟩ − ⟨z⟩2 , i.e. it represents the root-mean-square
deviation from the mean.
Invariably the product of these complementary quantities has dimensions of action, i.e.
Planck’s constant h or Joule-second. Action is an important variable in classical mechanics
as well as quantum mechanics. In classical mechanics one can derive Newton’s laws from
least action principle and it is often found to be more convenient. In the R path integral
formulation of quantum mechanics one starts with action defined as S = Ldt with L as
the Lagrangian. The probability amplitude for a given path is given by exp(iS/ℏ). From
this point of view Planck’s constant is also called quantum of action. In fact one can
define a rough criterion as follows:

16
 If for a physical system any natural dynamical variable which has the dimensions of
action assumes a numerical value comparable to Planck’s constant h then the behavior of
the system must be described by quantum mechanics. On the other hand if every variable
with action dimensions is very large in comparison to h, then the laws of classical physics
are valid with good accuracy.

2.5 Minimum energy estimates using uncertainty principle

It seems that the uncertainty principle cannot be violated and thus any system or experi-
ment will work within the limits dictated by this principle. For instance a particle confined
to certain space will have finite momentum spread and thus a finite kinetic energy. Also
if one uses a particle beam to probe the structure of various entities with required resolu-
tion, the probing particle will need to have de Broglie wavelength smaller than the desired
resolution, for example SEM. Thus one can estimate the minimum energy the probing
particle should have. Here we discuss another example that uses the uncertainty principle
to estimate the minimum energy that a particle in simple harmonic potential can have.

Figure 15: The probability distribution of particle wave in x and p space together with
the potential energy and kinetic energy in two spaces. A finite distribution of probability
away from origin leads to finite kinetic and potential energies in minimum energy state
which is also called ground state.

We begin with the total energy expression, E = (mω 2 x2 /2) + (p2 /2m). The particle
has to have a non-zero ⟨p2 ⟩ and ⟨x2 ⟩ in order to have finite ∆x.∆p. What all this means
is that the particle in its ground state will not be localized at one point in either x or in p.
So the particle will have a probability to take up various x or p values leading to a finite
spread. This aspect is driven by uncertainty principle and the underlying physics, as we
shall see more later, is basically driven by the wave-nature of particle. From symmetry and
for minimum energy we can assert that ⟨p⟩ = 0 and ⟨x⟩ = 0. Remember, ⟨p2 ⟩ = ∆p2 +⟨p⟩2
will assume a minimum value (for minimum KE) when ⟨p⟩2 is minimum, i.e. zero. The
same logic is used for potential energy term to deduce ⟨x⟩2 for minimum potential energy.
Thus we get ⟨p2 ⟩ = ∆p2 and ⟨x2 ⟩ = ∆x2 . We minimize total energy keeping the
minimum uncertainty product, i.e. ∆x.∆p = ℏ/2 or ∆p = ℏ/2∆x. These arguments lead
ℏ2
to E = 21 mω 2 x2 + 2m 1
4∆x2
. Minimizing with respect to ∆x, i.e. ∂E/∂∆x = 0 leads to
∆x = ℏ/2mω and eventually we get Emin = ℏω/2. This estimate of minimum turns out
2

to be exact for SHO as we shall see later from the detailed solution.

17
2.6 Matter waves and postulates of quantum mechanics
If we accept the wave description for matter particles, the natural question to ask is what
quantity or variable does this wave represent and what equation controls the dynamics
of this variable. Moreover, what is the prescription for deducing the experimentally
measurable quantities from this variable? For an em-wave we know that E ⃗ and B ⃗ describe
it in classical sense at least and Maxwell’s equations describe the dynamics of E ⃗ and B ⃗
fields. Guided by em-waves here are the starting postulates of quantum mechanics. This
part is more or less copied from Cohen-Tannoudji book. Here I list these postulates.
1) The particle and wave aspects of light (or matter particles) are inseparable. Light
behaves simultaneously like a wave and a flux of particles. The wave enabling us to
calculate the probability of manifestation of a particle.
2) Predictions about the behavior of a photon (or matter particle) can only be prob-
abilistic.
3) The information about the photon at time t is given by the wave E(⃗r, t) which
a solution of Maxwell’s equations. We say that this wave characterizes the state of the
photons at time t. E(⃗r, t) is the amplitude of a photon occupancy at time t and position
⃗r. That means that corresponding probability is proportional to |E(⃗r, t)|2 .
4) This analogy between light and matter is good background to talk about the wave-
function in analogy with E(⃗r, t). For particles behave like wave with λ = h/p and ν = E/h
as suggested by de Broglie. This also gives p = ℏk with k = 2π/λ, i.e. wave vector and
E = ℏω.
5) The quantum state of a particle is characterized by a wave-function ψ(⃗r, t) which
contains all the information it is possible to obtain about the particle.
6) ψ(⃗r, t) is the probability amplitude of particle’s presence. So the probability of
finding the particle in a small volume dτ at position ⃗r and at time t is given by dP (⃗r, t) =
|ψ(⃗r, t)|2 dτ . So |ψ(⃗r, t)|2 is the probability density.
R Since the probability of finding the
particle somewhere should be one, this means R 2 |ψ(⃗r, t)|2 dτ = 1. We can normalize it by
multiplying by a constant C such that C |ψ(⃗r, t)|2 dτ R = 1. In2 this case it is required
that any wave-function must be square integrable, i.e. |ψ(⃗r, t)| dτ should be finite.
7) With this description and as compared to classical mechanics, the particle now
is described by infinite number of variables, i.e. ψ(⃗r, t) is a continuous function while
classically we only need ⃗v and ⃗r at time t.
8) This is analogous to light and E(⃗r, t) in the sense that |E|2 represents photon’s
probability. Also just like E, ψ follows the superposition principle, i.e. ψ1 + ψ2 describes
the interference of two wave-functions of the same particle with |ψ1 + ψ2 |2 describing the
resulting probability density.
9) ψ(⃗r, t) allows one to find the probability of occurrence. The experimental verifica-
tion must than be founded on the repetition of a large number of identical experiments.
10) ψ(⃗r, t) is complex in quantum physics unlike E for em-waves where the complexity
of E helps mathematically is solving the wave equation systematically. Actually, the
precise definition of the complex quantum state of radiation can only be given in the
frame work of quantum electrodynamics, which is out of the scope of this course.
11) Measurements are very important in quantum mechanics as they seem to interfere
with the natural state of the system. So let’s discuss them more systematically.
12) A certain measurement gives results that belong to a certain set of characteristic

18
results called eigen-values, i.e. {a}. This set can be discrete or continuous depending on
the system and the type of measurement.
13) With each eigen-value there is an associated eigen-state wave-function ψa (⃗r). So
if a measurement yields a value ‘a0 ’, the wave-function afterwards would be ψa0 (⃗r). Any
further measurements, without any time evolution, will always give the same value ‘a0 ’.
It is always possible to P write a general wave-function as a linear combination of eigen-
funcions, i.e. ψ(⃗r, t0 )P= a Ca ψa (⃗r). Then the probability of a measurement giving result
‘a0 ’ is Pa0 = |Ca0 |2 / a |Ca |2 .

Illustration: The idea of measurement can be illustrated using polarizers in the way
of a single photon. Consider two polarizers with their easy-axes at an angle θ with respect
to each other. The are kept with their planes perpendicular to the light beam as shown
in figure.

Figure 16: Photon transmission through two polarizers with easy axis at different angles.
See text for details.

The first polarizer polarizes the light beam along x-direction so if the original beam was
unpolarized, half of the intensity would be lost. Now after second polarizer the intensity
would be further reduced by a factor cos2 θ. The remaining, proportional to sin2 θ, is
absorbed by the polarizer.
Now we reduce the intensity so much that only one photon crosses the polarizers at a
time. So after the photon crosses the first polarizer we know that its polarization is along
the x-axis. Now what happens when it crosses the second one? The probability that it
would cross is cos2 θ and the probability of its absorption is sin2 θ. But if we work with
one photon only than only one thing can happen, i.e. absorption or transmission. Now
if it gets transmitted it’ll have a polarization êp , i.e. if we put more polarizers after the
second one with their axes along êp , the photon will get transmitted through all of them
with 100% probability.
Thus the result of a measurement is either one of the eigen-values of the measure-
ment or the state gets annihilated completely in this particular case. So the measurement
disturbs the system in a fundamental way. If the result is certain eigen-value then the
resulting state is going to be the corresponding eigen-state after the measurement. By
knowing the original state, one can predict the probability of various eigen-values which
can then be verified by doing the experiment on several such identical particles or sys-
tems. In this context the Stern-Gerlach experiment is also relevant, which is dicussed in

19
Feynmann lectures, vol.3.
14) The equation describing the time evolution of ψ(⃗r, t) is the Schrödinger equation
given by,

∂ψ ℏ2 2
iℏ =− ∇ ψ + V (⃗r)ψ(⃗r, t). (18)
∂t 2m
We shall not attempt to prove it. It is one of the fundamental equations that could be
derived by higher level physics. However, historically it was just proposed based on the
de Broglie’s wave ideas and verified experimentally later on.
This equation has the following properties:
(A) It is linear and homogeneous in ψ, which means that the superposition principle
is valid, i.e. if ψ1 (x, t) and ψ2 (x, t) are two solutions of this equation than ψ(x, t) =
C1 ψ1 (x, t) + C2 ψ2 (x, t) is also a solution. Here C1 and C2 are two complex numbers.
(B) It is a first order differential equation in time. This is necessary if the state of the
particle at t0 (alone) is to determine its state later. If it were a second order equation in
time then one will need both ψ and ∂ψ | in order to find ψ(t).
∂t t0
(C) We also recall that for ψ(⃗r, t) to be a valid wave-function, it has to be square-
integrable.
If we compare with the usual wave-equation which is second order in time, here we have
genuinely complex solutions. But the similarities with the wave-equation are quite striking
and the intuition derived from wave phenomena is often correct in quantum mechanics but
not always. For instance the Huygen’s construction is not valid in quantum mechanics.

3 Free particle in one dimension

The time dependent Schrödinger equation for a free particle in one-dimension is

∂ψ ℏ2 ∂ 2 ψ
iℏ =− . (19)
∂t 2m ∂x2
In order to solve this equation we use separation of variables, which works as the space and
time derivative terms in above are decoupled. We write a possible solution as ψ(x, t) =
ψ1 (x)χ(t) leading to

iℏ ∂χ ℏ2 ∂ 2 ψ1
=− = E. (20)
χ ∂t 2mψ1 ∂x2
Here E is a constant which is actually the energy as it relates to the frequency of wave-
function evolution. The last equality follows as the first and second terms are dependent
on variables x and t and therefore they have to be equal to same constant. This leads
ℏ2 ∂ 2 ψ1
iℏ ∂χ
to two equations, namely, χ(t) ∂t
= E and − 2mψ 1 ∂x
2 = E. The first one has a solution

χ(t) = C1 exp(−iEt/ℏ) while the second one has solution ψ(x) = A1 eikx + B1 e−ikx with
k 2 = 2mE/ℏ. Here, E must be a positive number in order to have the expected wave-lik
solution for free-particle. Thus we see how E gets related to frequency and wave-vector
consistent with the de Broglie hypothesis, i.e. ω = E/ℏ and E = ℏ2 k 2 /2m. We can

20
eliminate E to get the dispersion relation ω = ℏk 2 /2m which is different from the em-
wave dispersion, i.e. ω = ck. The non-linear dispersion implies that the matter waves
are dispersive. Moreover, for matter waves, the phase velocity vp = ω/k = ℏ2 k/2m and
group velocity vg = dω/dk = dE/dp = ℏk/m = p/m or p = mvg .
For a given E the most general solution is

ψE (x, t) = Aei(kx−ωt) + Bei(−kx−ωt) (21)

with A and B as two independent constants. The first term represents a wave propagating
in +x direction while the second one is a wave moving along −x direction. In order to
proceed with a general solution for free particle let’s first discuss a special function called
Dirac delta function.

3.1 Dirac delta function: δ(x − x0 )

This is a rather special singular looking function. In fact, going by rigorous mathematics
it’s not a function it’s rather a distribution. Anyhow, we’ll not worry about this jargon
much. The Dirac delta function has two defining properties,
1) It’s zero everywhere except at one point x0 where it is singular, i.e.
(
0 for x ̸= 0
δ(x − x0 ) = (22)
∞ for x = 0

2) Its integral over a range including the singular point is one, i.e.
Z x0 +ϵ
δ(x − x0 )dx = 1 (23)
x0 −ϵ

Here ϵ can be an arbitrarily small number. Thus, a δ-function has dimensions of inverse of
it argument, i.e. in above case (Length)−1 . This is rather complex and it’s better to look
at this function as limit of a series of functions. I use two such constructions to illustrate
this.
1) We take a box-like function of height 1/2a and width 2a centered at origin, i.e.
(
1 1/2a for |x| < a
f (x) = Θ(a − |x|) = (24)
2a 0 for |x| > a

Here Θ is the step-function. Thus in the limit a → 0 this function assumes a very narrow
width and very large value at origin, see figure. At the same time it’s integral over a range
including origin is one. Thus we can assert δ(x) = lim f (x).
a→0
2) We take a limit of the sinc-function. This is rather useful for the context of Fourier
transform involved in the above free-particle wave-function discussion. We directly define
δ-function is k-space as,
sin kL
g(k) = (25)
πk

21
This function is oscillatory, though not periodic, with period ∆k = 2π/L. Its magnitude
away from origin is below 1/πk and its value at the origin is L/π. Here we take the
limit L → ∞. In this limit, the oscillation period approaches zero and it’s value at origin
diverges. So its average value in a small k-range, away from origin, will be zero.R Thus
it acquires a δ-function like appearance. To prove the second property we need g(k)dk
which we evaluate over full k-range with the understanding that the integral will get
zero contribution from region away from origin as the integrand oscillates with very small
period. Moreover, we’ll have to use the residue method to evaluate this integral.
We consider the following integral,
Z ∞ iz  iz 
e 1 e
dz = × 2πi Res = iπ. (26)
−∞ z 2 z=0 z

The last step uses the Rfact that exp(iz)/z only R ∞hasiza pole at originRand with residue 1.
∞ ∞
Finally using the fact −∞ (sin x/x)dx = Im[ −∞ (e /z)dz] we get −∞ (sin x/x)dx = π
R∞
and hence −∞ g(k)dk = 1.
A few other useful properties ofR δ-function are:
x
1) dxd
Θ(x − x0 ) = δ(x − x0 ) or −inf ty δ(x − x0 ) = Θ(x − x0 )
2) Rδ(−x) = δ(x), i.e. it’s a symmetric function,
3) g(x)δ(x−x P0 ) = g(x0 ), if the integration range encompasses x0 and zero otherwise.
4) δ(f (x)) = xn (1/|f ′ (xn )|)δ(x − xn ).
Here, the sum runs over xn which are the zeroes of f (x), i.e. f (xn ) = 0. The last one
also leads to δ(αx) = (1/|α|)δ(x).
The second
R ∞ ikxconstruction of Rδ-function discussed above is useful when one tries to
L
evaluate −∞ e dx. We have −L e dx = (1/ik)(eikL − e−ikL ) = 2 sin kL/k. So for
ikx

L → ∞, we get
Z ∞
sin kL
eikx dx = 2π lim = 2πδ(k). (27)
−∞ L→∞ πk

3.2 General time dependent wave-function for free particle

By superposition principle, any linear superposition of different E solutions also satisfies
time-dependent Schrödinger equation (TDSE). Thus the most general solution of TDSE
for a free particle in one dimension can be written as,
X   
px p2 t
ψ(x, t) = Ap exp i − .
p
ℏ 2m

Here, Ap is a complex number which depends on p and the above sum is carried out
over all (positive and negative) values of p. In fact, for infinite space in 1-D, p can take
continuous values and thus a general wave function is more appropriate to write as,
Z ∞   
px p2 t
ψ(x, t) = A1 g(p) exp i − dp. (28)
−∞ ℏ 2m

22
Here A1 is a normalization constant and g(p) is a complex function of p. At t = 0, we
have
Z ∞ h px i
ψ(x, 0) = A1 g(p) exp i dp. (29)
−∞ ℏ

Actually, this g(p) is a complex-function that represents wave-function in momentum

space and |g(p)|2 dp gives the probability of finding the particle’s momentum value between
p and p + dp. This eq. 29 basically is the defining relation for inverse Fourier transform
which helps us evaluate the real space wave-function from the k- or p-space wave function.
Using this we can evaluate A1 for both ψ(x, 0) and g(p) to be normalized. We use eq.
29 to write the expression for Fourier transform, i.e.
Z ∞ Z ∞ Z ∞
−ip′ x/ℏ ′
ψ(x, 0)e dx = A1 g(p)eipx/ℏ dpe−ip x/ℏ dx
−∞
Z−∞
∞
−∞
Z ∞ 
′
= A1 g(p) exp [i(p − p )x/ℏ]dx dp
−∞ −∞
Z ∞
= A1 2πℏδ(p − p′ )dp = A1 2πℏg(p′ )
−∞

leading to
Z ∞
1
g(p) = ψ(x, 0)e−ipx/ℏ dx. (30)
A1 2πℏ −∞

The above is the defining relation for Fourier transform. Our objective is to find A1 so
that both ψ(x, 0) and g(p) are normalized. For this,
Z ∞ Z ∞
|g(p)| dp =
2
g(p)g ∗ (p)dp
−∞ −∞
Z ∞ Z ∞  Z ∞ 
1 −ipx/ℏ ∗ ′ ipx′ /ℏ ′
= ψ(x, 0)e dx ψ (x , 0)e dx dp
(2πℏ|A1 |)2 −∞ −∞ −∞
Z ∞Z ∞ Z ∞ 
1 ∗ ′ [ip(x′ −x)/ℏ]
= ψ(x, 0)ψ (x , 0) exp dp dxdx′
(2πℏ|A1 |)2 −∞ −∞ −∞
Z ∞Z ∞
1
= ψ(x, 0)ψ ∗ (x′ , 0)2πℏδ(x′ − x)dx′ dx
(2πℏ|A1 |)2 −∞ −∞
Z ∞
1
= |ψ(x, 0)|2 2πℏdx
(2πℏ|A1 |)2 −∞
Z ∞
1
= |ψ(x, 0)|2 dx
2πℏ|A1 |2 −∞

Now for both g(p) and ψ(x, 0) to be normalized we should have |A1 |2 = 1/2πℏ. Thus we
write the full expressions for the Fourier transform and its inverse, respectively, as
Z ∞
1
g(p) = √ ψ(x, 0)e−ipx/ℏ dx (31)
2πℏ −∞

23
and
Z ∞
1
ψ(x, 0) = √ g(p)eipx/ℏ dp. (32)
2πℏ −∞

We can also write these using wave-vector k, instead of momentum p, as

Z ∞
1
g(k) = √ ψ(x, 0)e−ikx dx (Fourier Transform) (33)
2π −∞
and
Z ∞
1
ψ(x, 0) = √ g(k)eikx dk (Inverse Fourier Transform) (34)
2π −∞

Please note that Inverse Fourier Transform (IFT) of a Fourier Transform (FT) of a
given function leads to the original function. In fact FT (or IFT) is a linear transformation
implying many simplifications such √ as, FT[c1 ψ1 (x) + c2 ψ2 (x)]=c1 FT[ψ1 (x)]+c2 FT[ψ2 (x)].
Moreover, as defined above with 1/ 2π pre-factor, it preserves the norm of the function.
It turns out that it is a unitary transformation, which will become clearer later when we
discuss linear vector spaces.

3.3 Comparison of wave-equation with free-particle Schrödinger

equation
Here is an itemized comparison:
2 ∂2y
1) The wave equation, i.e. ∂∂t2y = v 2 ∂x 2 , is second order in both x and t.

2) Wave equation has general solutions of the form f (x ± vt) which is not possible for
Schrödinger equation.
3) Wave equation, being second order in time, requires two initial conditions to find
y(x, t). These can be y(x, 0) and ẏ(x, 0).
4) Boundary conditions with respect to x, for time independent equations, often have
similar nature. For example, the solution vanishes for both the particle in a well and the
electric field in a cavity at the boundaries. This leads to similar solutions for both cases.
5) Wave equation also has plane wave solutions of form e(ikx±ωt) with ω being real-
positive and k taking any real values. This follows from separation of variables. Since
the wave-equation
R∞ is a linear homogeneous
R∞ equation, a general solution can be written as,
y(x, t) = −∞ A− (k)ei(kx−ωt) dk + −∞ A+ (k)ei(kx+ωt) dk with ω = vk. The initial conditions
R∞ R∞
lead to y(x, 0) = −∞ [A+ (k) + A− (k)]eikx dk and ẏ(x, 0) = iω −∞ [A+ (k) − A− (k)]eikx dk.
Suppose Y (k) and Z(k) are Fourier transforms of y(x, 0) and ẏ(x, 0), respectively then
these can be used to get A+ (k) = [Y (k) + Z(k)/iω]/2 and A− (k) = [Y (k) − Z(k)/iω]/2.
These can now be used to find y(x, t).
6) In wave-equation solutions y is always a real number and complex notation is
only for mathematical convenience. Eventually one takes real or imaginary part of the
mathematical complex solution as valid physical solution. This is in contrast with the
Schrödinger equation.

24
3.4 Free-particle Gaussian wave-packet
Here we construct a localized wave-packet like solution to TDSE to simulate how a particle
like entity would evolve with time according to the TDSE. We discuss a specific wave-
packet called the Gaussian wave-packet, given by
 
a2
g(p) = A exp − 2 (p − p0 ) . 2
(35)
4ℏ
Here a is a constant with dimension of length. A is to be found from the normalization
condition,
Z ∞ Z ∞  
a2
|g(p)| dp = |A|
2 2
exp −2 2 (p − p0 ) dp = 1.
2
(36)
−∞ −∞ 4ℏ
We use the integral
Z ∞ p
exp [−α(ξ + β)2 ]dξ = π/α (37)
−∞

. This result is valid for complex α and β, if the Re[α] is positive so that the integral
converges. We can also differentiate this integral wrt α to derive
Z ∞
√
ξ 2 exp [−αξ 2 ]dξ = π/2α3/2 (38)
−∞

for β = 0 p
This helps us evaluate the integral in eq.36 to get |A| = (2π)−1/4 a/ℏ. Thus we get,
r  
1 a a2
g(p) = exp − 2 (p − p0 ) .2
(39)
(2π)1/4 ℏ 4ℏ
Now to work out the wave-function in x-space we need to find its inverse Fourier trans-
form using eq. .This is a bit cumbersome but straightforward after we use the Gaussian
integration identities. Here are the main steps,
 2 1/4 Z ∞  
a a2
ψ(x, 0) = exp − 2 (p − p0 ) + ipx/ℏ dp
2
8π 3 ℏ4 −∞ 4ℏ
 2 1/4 Z ∞ "  2 #  2 
a a2 2ℏx x ip0 x
= exp − 2 p − p0 − i 2 exp − 2 + dp
8π 3 ℏ4 −∞ 4ℏ a a ℏ
 1/4  2 
2 x ip0 x
= exp − 2 + . (40)
πa2 a ℏ
Remember this is the wave function at time t = 0 and we are yet to workout the non-zero
time wave-function. It is clear that this wave-packet is localized in both x and p spaces. In
p-space, g(p) real and symmetric about p0 while in x-space the wave-function is complex
and its real and imaginary parts are oscillatory with wave-vector p0 /ℏ and both have a
Gaussian envelope centered at x = 0. Thus the wave-function is spread over a finite x
and p range leading to uncertainty in both.

25
3.5 Uncertainty product for Gaussian wave-packet
RLet us evaluate thesep uncertainties
R explicitly. For ∆x2 = ⟨x2 ⟩ − ⟨x⟩2 , we have ⟨x⟩ =
∞ ∞
−∞
x|ψ(x, 0)|2 dx = 2/πa2 −∞ x exp (−2x2 /a2 )dx = 0. The integral here gives zero as
the integrand is an odd function of x.
Now,
Z ∞
⟨x ⟩ =
2
x2 |ψ(x, 0)|2 dx
r−∞ Z ∞ r √
2 2 π a2
= x 2
exp (−2x 2
/a2
)dx = × = .
πa2 −∞ πa2 2.(2/a2 )3/2 4
p
Thus we get ∆x ⟨x2 ⟩ − ⟨x⟩2 = a/2.
Now we go after ∆p2 = ⟨p2 ⟩ − ⟨p⟩2 . For this,
Z ∞ Z ∞  
a a2
⟨p⟩ = p|g(p)| dp = √
2
p exp − 2 (p − p0 ) dp
2
−∞ 2πℏ −∞ 2ℏ

Let’s make a change of variable from p to q = p − p0 to get,

Z ∞   Z ∞  
a a2 2 ap0 a2 2
⟨p⟩ = √ q exp − 2 q dq + √ exp − 2 q dq
2πℏ −∞ 2ℏ 2πℏ −∞ 2ℏ

Clearly the first term in above vanishes and the second uses the Gaussian integral, eq.
37, to obtain,
 1/2
p 2πℏ2
⟨p⟩ = (ap0 / 2/πℏ) = p0 .
a2

Finally, we need to find ⟨p2 ⟩. We write,

Z ∞  
a a2
⟨p ⟩ = √
2
p exp − 2 (p − p0 ) dp
2 2
2πℏ −∞ 2ℏ

Again let’s make a change of variable from p to q = p − p0 to get,

Z ∞  
a a2 2
⟨p ⟩ = √
2
(p0 + q + 2p0 q) exp − 2 q dq
2 2
2πℏ −∞ 2ℏ
" √ √ #
a 2 2πℏ 2π ℏ2
= √ p0 + 2
+ 0 = p0 + 2 .
2πℏ a 2(a2 /2ℏ)3/2 a

Here again use has been made of eq. 37 and 38 in evaluating above integral. Thus
we get ∆p2 = ⟨p2 ⟩ − ⟨p⟩ = p20 + (ℏ2 /a2 ) − p20 = (ℏ2 /a2 ). Hence, for this Gaussian wave-
packet, the uncertainty product ∆p.∆x = (ℏ/a).(a/2) = ℏ/2. This is the minimum
possible uncertainty product. In fact, one can prove rigorously that the above Gaussian
is the only wave-packet that leads to the minimum uncertainty product. In fact, not all
Gaussian wave-packets will lead to the same outcome.

26
3.6 Time evolution of the Gaussian wave-packet
We follow the general strategy of solving TDSE for free particle for given initial ψ(x, 0).
In fact we started with a g(p) and worked out the ψ(x, 0). Now, according to earlier
discussion as per eq. 28, the corresponding time dependent wave-function is given by,
Z ∞  
1 px p2 t
ψ(x, t) = √ g(p) exp i − i dp. (41)
2πℏ −∞ ℏ 2mℏ
h 2 i p
Here, g(p) = A exp − 4ℏ a
2 (p − p 0 ) 2
with A = (2π)11/4 aℏ . The mathematics of the evalu-
ation of the above integral is rather tedious though doable analytically. It involves a few
integrals that use eqs. 37 and 38 with complex α and β. You can work it out if you feel
up to it. I’ll give the final result here,
 1/4 r  2 2  
2 a a p0 x − i(a2 p20 /2ℏ)
ψ(x, t) = exp − 2 exp − 2 . (42)
π a2 + (2iℏt/m) 4ℏ a + 2i(ℏt/m)

This looks rather complicated. We can workout the time dependence of probability dis-
tribution in real space, which gives,
s  
∗ 2 (x − p0 t/m)2
P (x, t) = ψ(x, t)ψ (x, t) = exp − . (43)
πa(t) a(t)2

Here,

4ℏ2 t2
a(t)2 = a2 + (44)
m2 a2
We notice that |g(p)|2 , i.e. probability distribution in p-space, does not change while
P (x, t) changes with time. This also means that uncertainty ∆p = ℏ/a remains same,
while the uncertainty ∆x = a(t)/2 is time dependent. Thus the product,
 1/2
ℏ 4ℏ2 t2 ℏ
∆x.∆p = 1+ 2 4 ≥ . (45)
2 ma 2

The uncerainty product is minimum at t = 0. For large t, ∆x = (ℏt/ma) = (∆p/m)t =

∆vt. The wave packet disperses as different p-components of the wave move with different
velocities.
A few remarks: The Mathematica simulation in lecture on the evolution of a Gaus-
sian wave-packet illustrates many aspects of Gaussian wave-packet of matter waves. Some
of these are:
1) The wave-packet moves with group velocity vg = dω/dk = p/m and not with phase
velocity vp .
2) The wave-packet disperses with a reduction in spread as time progresses for negative
times reaching a minimum spread at zero time and then the spread increases again for
positive time.
3) There is no change in the momentum uncertainty, i.e. ∆p, with time.

27
 4) One can also make out how the small λ plane-waves move faster than the large λ
leading to dispersion or spread in the wave-packet.
5) One can understand the increase in spread easily by making a parallel with an
athletic race. In a race all runners start from the same start line but after race starts
there position has a spread as all the runners run with different speed or in other words
there is a spread in velocity. One can easily argue that the real space spread in runners
position, i.e. ∆x, will be given by ∆x = ∆vt. This is the case for Gaussian wave packet
for large times where ∆x = ∆p/m as ∆p = ℏ/a.
6) We can estimate this rate of spread in x-space for macroscopic objects. So for m =
1 µgm and a = 1 µm we get d∆x/dt = ∆p/m = ℏ/ma ∼ 10−22 m/s. This is extremely
small as compared to the particle size and macroscopic velocity scales (m/s). It’ll take
about 1016 s or 109 years to see doubling of the size due to dispersion.
Similarity to diffusion: It turns out that the Schrödinger equation for a free particle,
2 2
i.e. ∂∂xψ2 = −i 2m
ℏ
∂ψ/∂t has similar structure as the diffusion equation, i.e. ∂∂xT2 = D1 ∂T /∂t.
κ
Here T , for instance, can be temperature where thermal diffusivity D = σc with κ as
thermal conductivity, c as specific heat and ρ as density. The diffusion equation applies
to many phenomena such as diffusion of atoms or chemical species, charge, heat. This
equation has solutions similar ”diffusive” (similar to ”dispersive”) solutions when a local-
ized distribution at t = 0 spreads as time progresses. In fact the mathematics of solving
the diffusion equation is similar to that of the Schrödinger equation for free particle. One
difference in diffusion case is as time progresses the spatial spread always increases while
for matter waves it can increase or decrease both as we see above.

4 Some more formalism

Before we move on to the topic of one-dimensional potentials and how one can approach
the quantum dynamics through the solutions of time-independent Schrödinger equation
(TISE) we need to discuss a few more topics that are related to the postulates.

4.1 Expectation values, Hermitian operators and matrix ele-

ments
We see that the wave function ψ(x) leads to a probability distribution P (x) = |ψ(x)|2
in real space and thus one
R can find the Raverage values of space dependentR quantities of
∗
interest,
R such as ⟨x⟩ = x|ψ(x)|2
dx = xψ (x)ψ(x)dx or ⟨f (x)⟩ = R f (x)|ψ(x)|2
dx =
∗ ∗
f (x)ψ (x)ψ(x)dx. Thus one can find the average potential ⟨V ⟩ = ψ (x)V (x)ψ(x)dx.
We call ⟨f (x)⟩ψ as the ”expectation value” of f over wave-function ψ(x).
Similarly we could find the wave function g(p) in p-spaceR by Fourier transform
R ∗ leading
to the probability distribution in p-space and thus ⟨p⟩ = p|g(p)|
R
2
dx = g (p)pg(p)dp.
It turns out that we can also write this in x-space as ⟨p⟩ = ψ ∗ (x)(−iℏ)(∂ψ(x)/∂x)dx.
Thus we surmise that in x-space we can write p = −iℏ(∂/∂x). Thus −iℏ(∂/∂x) is called
momentum operator. Similarly we can write the total energy operator, i.e. Hamiltonian,
as H = (p2 /2m) + V (x)R and so one can find the expectation value
R ∗ of total energy (kinetic
∗
+ potential) as ⟨H⟩ = ψ (x, t)[(p /2m) + V (x)]ψ(x, t)dx = ψ (x, t)(iℏ∂/∂t)ψ(x, t)dx.
2

28
The last equality follows from Schrödinger equation. So iℏ(∂/∂t) is equivalent to the
energy operator.
Another entity that we introduce here is the matrix element of an operator. We’ll
discuss a more detailed approach to such entities later when we discuss linear vector
spaces. However, we need these to develop the machinery of quantum mechanics further.
We define the matrix element of an operator
R ∗ ‘A’ between two states described by wave-
functions ψ(x) and ϕ(x)
R as ⟨ψ|A|ϕ⟩ = ψ (x)Aϕ(x)dx. This is different from the matrix
element ⟨ϕ|A|ψ⟩ = ϕ∗ (x)Aψ(x)dx as in the former case ‘A’ operates on ϕ(x) while in
later it operates on ψ(x). The expectation value defined above is a special matrix element,
i.e. ⟨A⟩ψ = ⟨ψAψ⟩.
Another concept is that of Hermitian operators. Again this concept will be discussed
in more detail later. It turns out that all eigen-values of a Hermitian operator are real
or vice-versa, i.e. any operator with all eigen-values real is Hermitian. Thus in quantum
mechanics any observable, such as position, momentum, energy, is associated with a
Hermitian operator. We need to define this Hermitian property mathematically. An
operator ‘A’ is called Hermitian if its matrix element over any arbitrary wave-functions
ϕ(x) and ψ(x) satisfy: ⟨ψ|A|ϕ⟩ = ⟨ϕ|A|ψ⟩∗ or in another way
Z Z Z
ψ (x)Aϕ(x)dx = ( ϕ (x)Aψ(x)dx) = [Aψ(x)]∗ ϕ(x)dx.
∗ ∗ ∗
(46)

4.2 Time independent Schrödinger equation

We have already seen this for the free particle. Now for V (x) ̸= 0, the TDSE is
iℏ∂ψ(x, t)/∂t = Hψ(x, t) with H = (p2 /2m) + V (x). For time-independent potentials
V (x), we can use separation of variables. So we use ψ(x, t) = ϕ(x)χ(t) to write
1 iℏ dχ
Hϕ(x) = = constant = E
ϕ(x) χ dt
Therefore, we get HϕE (x) = EϕE (x) and χE (t) = exp (−iEt/ℏ). Here ϕE (x) is specific
solution of TISE HϕE (x) = EϕE (x) with energy eigen value E. The TISE expands into
ℏ2 d2 ϕ
− + V (x)ϕ(x) = Eϕ(x) in 1D
2m dx2
ℏ2 2
− ∇ ϕ(⃗r) + V (⃗r)ϕ(⃗r) = Eϕ(⃗r) in 3D
2m
In fact there may be more than one independent solution for ϕE (x) for a given energy E.
An example of this is the ±p plane wave solutions for free-particle which have the same
energy p2 /2m. These are called degenerate (smae energy) eigen-states. We use an extra
index α in ϕEα to denote all such independent solutions that are degenerate. The most
general solution of the TDSE will be
X
ψ(x, t) = AEα ϕEα (x) exp (−iEt/ℏ) (47)
E,α

The eigen state ϕE (x) is also called a stationary state as it does not evolve with time except
for a phase factor. For a given initial state ψ1 (x, 0) at t = 0 if one wants to find its time

29
 P
evolution one has to find the complex coefficients AEα such that ψ1 (x, 0) = AEα ϕEα (x).
One can then use these AEα in eq. 47 to write the time-dependent solution.
The fact that any arbitrary ψ1 (x) (physically acceptable) can be written as a linear
superposition of ϕEα for a general Hamiltonian is not trivial. But it turns out that
these ϕEα always form a complete set. Thus these ϕEα are called Eigen (characteristic)
functions.
The fixed energy states have special significance because one can observe transitions
between these states and the energy difference between these states is easily observed as
emitted (or absorbed) radiation at specific frequencies.

30
 Some remarks on TISE:
1) TISE has no ‘i’ so its solution need not be complex but it can be if convenience
dictates. For example for free particle we chose exp (±ikx) but we could have chosen
sin kx and cos kx as well.
2) An eigen-state wave-function ϕ(x) must be finite, single valued, continuous.
3) dϕ/dx must also be finite, single valued and continuous.
These properties of TISE and ϕE (x) sometimes (for bound states) force that the
solutions of TISE are found at certain energies only. This leads to quantized energies for
bound states as we’ll see soon. A good reference to see how this happens is sec. 5.7 of
Eisberg and Resnick.
It should also be pointed out that some of the mathematical restrictions are marginally
violated for ideal (unphysical) potentials that go to infinity or have a step jump. For
instance if potential abruptly jumps to infinity at some point, as for infinite well, dψ/dx
can be discontinuous.

4.3 Probability Current

The TDSE in 1-D is,

ℏ2 ∂ 2 ψ ∂ψ
Hψ = − 2
+ V (x)ψ(x) = iℏ
2m ∂x ∂x
The probability density ρ(x, t) = |ψ(x, t)|2 assuming the wave-function ψ(x, t) to be nor-
malized. As a result of time evolution of ψ the probability density will change with time.
However, when the probability in certain given region changes we expect to see a flow
of this probability at the boundaries. This is a local conservation of probability. This
is similar to charge conservation in the sense that when the charge contained in certain
region of space changes with time we expect to see a charge current at the boundary of
∂ρ
this region. This leads to the continuity equation: ∂tQ + ∇.⃗ J⃗Q . We are after a similar
concept here. We have,
∂ρ ∂ ∂ψ ∂ψ ∗
= (ψψ ∗ ) = ψ ∗ +ψ
∂t ∂t ∂t ∂t
Using the TDSE for time derivatives this gives,
 
∂ρ 1 −1
= ψ ∗ Hψ + ψ Hψ ∗
∂t iℏ iℏ
Rx
Thus the probability for finding the particle between x1 and x2 , i.e. P (x, t) = x12 ρ(x, t)dx,
will change with time as
Z x2 Z     
∂P ∂ρ 1 x2 ℏ2 ∂ 2 ψ ∗ ℏ2 ∂ 2 ψ ∗ ∗
= dx = − +Vψ ψ − − + V ψ ψ dx
∂t x1 ∂t iℏ x1 2m ∂x2 2m ∂x2
Z x2  
ℏ 2
∗∂ ψ ∂ 2ψ∗
=− ψ −ψ dx
2im x1 ∂x2 ∂x2

31
We use integration by parts to get
 Z   Z x2
∂P ℏ ∗ ∂ψ ∂ψ ∗ ∂ψ ∂ψ ∗ ∂ψ ∗ ∂ψ
=− ψ − dx − ψ − dx
∂t 2im ∂x ∂x ∂x ∂x ∂x ∂x x1
 
∗ x2
ℏ ∂ψ ∂ψ
=− ψ∗ −ψ
2im ∂x ∂x x1
= −[S(x2 ) − S(x1 )]

Here, we have used,

   
ℏ ∗ ∂ψ ∂ψ ∗ ℏ ∗ ∂ψ
S(x) = ψ −ψ = Im ψ (48)
2im ∂x ∂x m ∂x
R x2
We call the above S(x) as probability current density. This leads to ∂P
=− ∂S
dx =
R x2 ∂ρ ∂t x1 ∂x

x1 ∂t
dx or in other words,

∂ρ ∂S
+ =0 in 1-D
∂t ∂x
∂ρ ⃗ ⃗
+ ∇.S = 0 in 3-D (49)
∂t
In 3D this is actually a vector quantity. It basically represents probability
h i flux, i.e.
ℏ
⃗ = Im ψ ∇ψ ∗ ⃗ . Eq. 49 is
probability flow per unit area per unit time. In 3D, we have S m
the continuity equation describing local probability conservation just like the continuity
equation for charge conservation in em-theory.

4.4 Time-energy uncertainty

Just like p and x, E and t are also complementary variables and the fact ∆x.∆p ≥ ℏ/2
is a consequence of associating λ with p, the time-energy uncertainty, ∆E.∆t ≥ ℏ/2 is
also a consequence of associating ν with E. Unlike ∆x it is difficult to define ∆t precisely
as t is a parameter rather than an observable. However, if one finds examples where
∆x.∆p ≥ ℏ/2, this can be translated into ∆E.∆t ≥ ℏ/2 as discussed in one example
below. One can illustrate time-energy uncertainty in several ways:
1) We recall from classical dynamics of a damped harmonic oscillator that its oscilla-
tions decay over a time scale τ dictated by damping. If the same oscillator is driven with
frequency ν near resonance, the response of the oscillator as a function of drive frequency
exhibits a peak at resonance with width ∆ν, which again is dictated by damping that
leads to certain quality factor. Fig. 17 illustrates how these τ and ∆ν are inversely related
so as τ.∆ν ∼ 1. This simple example already captures the time-energy uncertainty. In
QM one associates E with ν, i.e. E = hν.
2) A wave-function made up of different energy eigen-states spanning an energy range
∆E will evolve significantly over a time ∆t given by ∆E.∆t ∼ ℏ. For stationary states,
i.e. eigen-energy states, this time evolution scale is ∞ and ∆E = 0. In QM, we write the
general solution of TDSE as per eq. 28. Let’s look at a state made by superposing two
energy eigen-states, i.e. ψ(x, t) = ϕE1 (x) exp (−iE1 t/ℏ)+ϕE2 (x) exp (−iE2 t/ℏ). This state

32
Figure 17: Illustration of time-frequency uncertainty in a Harmonic oscillator. The
damped motion in time-domain in the left panel and the driven motion in frequency
domain is consisten with ∆t.∆ν ∼ 1
.

evolves significantly over a time scale ℏ/|E1 − E2 | i.e. ℏ/∆E. For instance probability of
measuring the system in two orthogonal states ϕE1 (x) + ϕE2 (x) and ϕE1 (x) − ϕE2 (x) works
out to be cos2 (∆Et/ℏ) and sin2 (∆Et/ℏ), respectively. These have significant evolution
over time scale ∆t ∼ ℏ/∆E. This idea can also be mapped to a classical coupled harmonic
oscillator system.
3) In nature when atoms emit em-radiation at characteristic frequency the emission
line has a natural line-width ∆λ. This measured line-width can arise from extrinsic factors
such as Doppler broadening and from the intrinsic lifetime τ of the excited states. This
τ and ∆E = hc∆λ/λ2 are related by ∆Eτ ∼ ℏ. Typical values of τ are in 10 ns range
giving ∆λ/λ ∼ 10−10 for ν ∼ 101 4 Hz.
4) Let’s try to measure the momentum of a free particle of mass m by observing its
displacement over time ∆t, i.e. ∆t = ∆x/v = m∆x/p assuming that the particle moves
by ∆x in ∆t. Now suppose the uncertainty in momentum measured in this way is ∆p
then ∆E = ∆(p2 /2m) = p∆p/m. Thus ∆E.∆t = (p∆p/m).(m∆x/p) = ∆p.∆x ≥ ℏ/2.
5) Suppose if one tries to measure E by looking at the time evolution of the wave
function and finding the frequency with which it is evolving. This sounds difficult in QM
but in classical oscillators one does measure the frequency in this way. If one measures
the behavior over time ∆t then the accuracy (or uncertainty) in frequency measurement
will ∼ 1/∆t as dictated by the Fourier transform in time domain. This also leads to
∆E.∆t ∼ ℏ
6) Another interpretation relates to an explanation of quantum tunneling where there
is an apparent violation of energy conservation, at least for a short time, when particle
crosses the barrier through quantum tunneling. It seems that one can actually create or
destroy ∆E energy for a time period ∼ ℏ/∆E. The fact that a particle goes across a
barrier seems to violate the energy conservation. A reconciliation is that an an energy
∆E can temporarily be borrowed for a time ∆t ≤ ℏ/∆E if this time is enough for going
across. We should understand that this extra energy is temporary and tunneling is a
perfectly elastic process.

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4.5 Heisenberg equation of motion
In QM any given measurable
R ∗ quantity corresponds to an operator, say B, whose expec-
tation value ⟨B⟩ = ψ (x, t)Bψ(x, t)dx is a useful and measurable quantity. Its time
evolution is also important. It turns out that finding out how this expectation value
does not necessarily require solving for the time dependent wave-function. This can be
obtained using the Heisenberg equation of motion as we discuss here. ⟨B⟩ for a time-
independent operator will change with time as for a general state ψ(x, t) changes with
time. As mentioned earlier, any measurable quantity will correspond to a Hermitian
operator as defined by eq. 46. We have,
Z Z  ∗ 
∂ ∂ ∗ ∂ψ ∗ ∂B ∂ψ ∗
⟨B⟩ = (ψ Bψ) dx = Bψ + ψ ψ+ ψ dx
∂t ∂t ∂t ∂t ∂t
Using the TDSE for the first and third term, we get
Z  
∂ ∂B 1 ∗ ∗ 1
⟨B⟩ = ⟨ ⟩+ − (Hψ )Bψ + ψ B Hψ dx
∂t ∂t iℏ iℏ
R R
Now since
R H is HermitianR we use eq. 46 so that (Hψ)∗ ϕdx = ψ ∗ Hϕdx with ϕ = Bψ
to get (Hψ)∗ Bψdx = ψ ∗ HBψdx. We also assume B to be time independent. Thus
the above expression simplifies to
Z Z
∂ 1 ∗ ∗ 1
⟨B⟩ = [ψ BHψ − ψ HBψ] dx = ψ ∗ [BH − HB] ψdx
∂t iℏ iℏ
Defining the commutator [B, H] = BH − HB, we get the Heisenberg equation of motion:
∂ 1
⟨B⟩ = ⟨[B, H]⟩ (50)
∂t iℏ
Here are a few consequences and remarks related to this equation:
1) When [B, H] = 0 we get ∂t ∂
⟨B⟩ = 0, i.e. B is a constant of motion. Thus the oper-
ators that commute with Hamiltonian are important as they define constants of motion.
Usually such an operator describes certain symmetry of the system (or Hamiltonian). It
often helps to find such operators first to solve for eigen-states of H. Since H commutes
with itself so energy expectation value is a constant of motion.
2) We can also prove that the expectation value of any operator over an eigen-state
of H is independent of time.
3) Another consequence of commutator being zero is one can always find functions
which are simultaneous eigen-functions of such commuting operators. This, as we shall
see, helps in accounting for the degenerate eigen-states of H.

5 Bound state solutions of TISE in 1D

The bound state solutions are found by solving the TISE for ψ(x). The admissible so-
lutions must ensure that ψ(x) and dψ/dx are continuous everywhere and ψ(x) is square
integrable. The latter implies that ψ(x) → 0 as x → ∞. AS discussed earlier the conti-
nuity of dψ/dx is sometimes violated for ideal mathematical potentials that have infinite

34
jump at a point. These potentials are only to be looked at as limiting cases of real
potentials and dψ/dx is never discontinuous for physically meaningful potentials. The
discontinuity of dψ/dx at such points can be easily understood if one writes TISE as,
d2 ψ 2m[V (x)] − E]
= ψ(x).
dx 2 ℏ2
We can see that when V (x) jumps to ∞ at a point for finite E, d2 ψ/dx2 is infinite at such
points which indicates a discontinuity in dψ/dx.

5.1 Infinite potential well

The infinite potential well is defined by,
(
0 for 0 < x < L
V (x) =
∞ otherwise

Going with the general strategy stated above ψ(x) must be zero for x < 0 and x > L.
For 0 < x < L, we have
d2 ψ 2mE
= − 2 ψ(x) = −k 2 ψ(x)
dx 2 ℏ
with k 2 = 2mE/ℏ2 as a positive quantity. One cannot find any meaningful solutions for
E < 0. The solution for this is ψ(x) = A sin kx + B cos kx. For ψ(x) to be continuous,
we should have:
(i) ψ(0) = 0, which leads to B = 0,
(ii) ψ(L) = 0 implying sin kL = 0 as A ̸= 0 for non-trivial solution. This implies
kL = nπ. RL
Thus we get ψ(x) = A sin (nπx/L). To normalize ψ(x), we have |A|2 0 sin2 (nπx/L)dx =
p
1, which leads to |A| = 2/L. As stated earlier the phase of A cannot be determined and
we take it as zero as a convention. We also see that values of k are quantized in integer
multiple of nπ leading to permitted energy values as En = n2 π 2 ℏ2 /2mL2 . To summarize:
r  nπx 
2 n2 π 2 ℏ2
ψn (x) = sin and En = (51)
L L 2mL2
Here are a few remarks on this problem:
1) Energies are discrete, which is different from the classical expectation of continuous
energies.
2) Minimum energy, i.e. π 2 ℏ2 /2mL2 is non-zero which is different from the classical
expectation of zero.
3)En ∝ n2 so (En+1 − En ) ∝ n,R i.e. energy separation increases with n
4) ψn (x) are orthonormal, i.e. ψn∗ (x)ψm (x)dx = δnm with δnm is Kronecker delta.
5) The plots of ψn (x) has n − 1 nodes (other than the two extreme ones). This is a
general feature of bound states, i.e. as E increases number of nodes increase.
p
for ψn (x) work out as ∆pn = nπℏ/L and ∆xn = L (1/12 − (1/2n2 π 2 )).
6) The uncertainties p
Thus, ∆pn .∆xn = nπℏ (1/12) − (1/2n2 π 2 ). So uncertainty product increases with n.
For n = 1, ∆pn .∆xn = 0.57ℏ > ℏ/2

35
 7) Since V (x) is symmetric about x = L/2 so ψn are either symmetric or antisymmetric
about x = L/2. This happens as H commutes with the ‘inversion about L/2’ operator
and there is no degeneracy.
8) One can write any general wave-function that vanishes at x = 0 and x = L as
a linear superposition of ψn (x). This can be seen easily here using the idea of Fourier
series. Let’s discuss an example wave-function: ψ(x) = A sin3 πx/L. Here, A is the
normalization
√ factor. We can easily see that the normalized wave-function is given by:
ψ(x) = (1 10)[ψ3 (x) − 3ψ1 (x)] by using identity sin 3θ = 3 sin θ − 4 sin3 θ. Thus for this
case the probability to find the particle in E1 and E3 states will be 9/10 and 1/10, respec-
tively. This also leads to an energy expectation value of (9E1 + E3 )/10 = 9π 2 ℏ2 /10mL2 .
Simulating a classical particle: Clearly, the above stationary eigen-states are far
from classical behavior. A natural question then is: how do we construct a classical-like
solution using these eigen-state wave-functions? A classical particle in such box-potential
is expected to elastically bounce from the two hard walls of the potential well with constant
speed in-between. We construct a superposition wave-function which is localized at a given
time and its time evolution is consistent with the classical expectation. Here is such a
wave-function:
X
N +(∆N/2)  
nα ℏπ 2
ψ± (x, t) = sin (nπx/L) exp (±inaπ) exp −i t .
2mL2
N −(∆N/2)

Here α = 2. This actually gives a wave packet centered at x = a and moving to the left or
right, depending on the sign chosen in the middle exponential term. We choose the unit
of time as τ = (4mL2 /h = 1. This makes the exponent of the last exp term as −iπnα t/τ .
For L = 1 cm and m = 1 gm we get τ ∼ 6 × 1026 . The center of the wave function moves
at speed vN = N ℏπ/mL. This just means that the magnitude of speed v0 corresponding
to N = 1, i.e. v0 = ℏπ/mL, is extremely small. For above parameters (1 gm and 1 cm)
we get v0 = 3.3 × 10−29 m/s. So for a classical particle to move at noticeable speed, say
10−3 m/s, the principal quantum number (N ) will have to be ∼ 3 × 1025 , which is huge.
The parameter ∆N is the spread in N corresponding closely to uncertainty in momen-
tum. This is required to make a localized wave-packet representing a classical particle. In
fact the magnitude of the width of the wave-packet in real-space is proportional to 1/∆N .
As time passes this wave-packet’s evolution consists of its motion with reflection at the
walls and dispersion (spread). The time scale of wave-packet motion over the width of
the well is given by L/N v0 while time taken to disperse it in the whole well would be
∼ L/(∆N v0 ). The latter can be very large as compared to the former if ∆N/N is very
small, which would be the case for a classical particle.
All the above features, namely, motion, reflection, dispersion, etc., can be easily
demonstrated with the above wave-packet using Mathematica. One can also see the
effect of various parameters on motion and dispersion. It is worthwhile to notice how the
small wavelength (or sharper) features move faster than the large wavelength components.
It is also interesting to see the effect of the value of α. The wave-packet becomes
non-dispersive for α = 1. Further one can see the change in the nature of dispersion
when α is changed from 1.01 to 0.99. In this case one can see how the sharp features lead
in the former case while the broad tail legs and vice versa for the latter case. It is also
interesting to see the time evolution from a negative t.

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 In the Mathematica code one has to run the first half of the code to create the matrix
that stores the complex time dependent wave-packet at different times. This is computa-
tion intensive and for large ∆N it takes longer as the series to be summed has more terms.
After this matrix is created one can run the animation part to get the time evolution of
the wave-function.

5.2 Piecewise constant potentials in 1D

Solving for the bound states of an arbitrary 1D potential requires solving the TDSE for
which there is no general way and thus there are few analytically solvable 1D potential
bound states. Harmonic oscillator is one of them but that also involves special functions.
However, for a potential which is piecewise constant, i.e. V (x) is made up of constant
value segments as illustrated in Figure 18. In such case we can formulate a general strategy
to put down the solution and the boundary conditions that eventually lead to equations
which lead to the eigen-energies of the bound states and corresponding wave-functions.
These equations may or may not be analytically solvable.

Figure 18: Piecewise constant potential V (x) with a bound state of eigne-energy E.

The bound states will exist for energy E values which are between the minimum of
potential and the maximum or the potential at infinity. For some x-ranges V (x) < E
while for others V (x) > E and these two types of regions will have different types of
solutions. Suppose V (x) = V1 < E for x1 < x < x2 then we get the TISE as,
2m 2m
ψ ′′ = − (E − V1 )ψ(x) = −k12 ψ(x) with constant k12 = 2 (E − V1 ) > 0.
ℏ2 ℏ
Thus we can write the solution for this x-range in three equivalent ways with two un-
knowns,
ψ(x) = A1 exp(ik1 x) + B1 exp(−ik1 x) OR
ψ(x) = C1 sin k1 x + D1 cos k1 x OR
ψ(x) = F1 sin k1 x + δ1 .
For region, say x2 < x < x3 , V (x) = V2 > E then we get the TISE as,
2m 2m
ψ ′′ = (V2 − E)ψ(x) = −κ22 ψ(x) with constant κ22 = 2 (V2 − E) > 0.
ℏ2 ℏ

37
In such regions we can write the solution in the following three equivalent ways with two
unknowns,

ψ(x) = A2 exp(κ2 x) + B2 exp(−κ2 x) OR

ψ(x) = C2 sin κ2 x + D2 cos κ2 x OR
ψ(x) = F2 sin κ2 x + δ2 .

Here A1 , A2 , B1 , B2 , etc. are complex constants to be found from boundary conditions.

One can also choose to work with either k or κ for all regions and in this case these can
take imaginary values also. With these one has to satisfy the boundary conditions at
the boundaries between various constant potential regions. For the above case, one such
boundary is x = x2 . Each boundary leads to two equations from continuity of ψ(x) and
ψ ′ (x).
For bound states, the wave function for far left, i.e. x → −∞, must be either zero, if
the potential is infinite in this region or it is finite then it’ll have a form exp(κL x) with
appropriate κL . Similarly for far right, i.e. x → −∞, the solution can be either zero or
of form exp(−κR x). Also if V (x) becomes infinite in certain regions ψ(x) must vanish in
such regions.
Another remark that I want to make at this stage is about the zero of energy. We
have the freedom to choose the zero of energy and potential, as long as we choose one
and the same for both. Different problems may make a particular choice of this zero more
convenient than others. One can see that this choice does This might be dictated by the
problem

38