QSP – Unit 2

• The paradox described by Heisenberg’s uncertainty principle and the wavelike nature
of subatomic particles such as the electron made it impossible to use the equations
of classical physics to describe the motion of electrons in atoms.
• Scientists needed a new approach that took the wave behavior of the electron into
account.
• In 1926, an Austrian physicist, Erwin Schrödinger (1887–1961; Nobel Prize in Physics,
1933), developed wave mechanics, a mathematical technique that describes the
relationship between the motion of a particle that exhibits wavelike properties (such
as an electron) and its allowed energies.
• In doing so, Schrödinger developed the theory of quantum mechanics, which is used
today to describe the energies and spatial distributions of electrons in atoms and
molecules.
• Quantum Mechanics (Wave –Mechanics)
• In classical mechanics the motion of particle is usually described using the time
dependent position x(t) as the dynamical variable.
• F = ma = mẍ.
• In wave mechanics the dynamical variable is a wave function.
• The wave function depends on position and time and it is a complex number.
Quantum mechanics was developed in 1925 by Schrödinger and Heisenberg.
• Schrödinger method involves partial difference equation.
• Heisenberg’s method employs matrices.
• Since former involves the solution of wave equations, it is also called wave-
mechanics; and latter, which involves matrices, is called matrix mechanics. Though
both of them are equivalent.
• In this syllabus we shall mostly confine ourselves to wave-mechanics only.
• The Schrödinger Equation
• If a mass (particle) ‘m’ is moving along x-axis subject to a specified
force F(x,t).
• Classical mechanics looks to determine the position of the particle at
any given time x(t). Once we know this information v, p etc. can be
determined.
• F = ma
𝑑2 𝑥 𝜕𝑣
𝑚 2 = −
𝑑𝑡 𝜕𝑥
• Where, we have assumed i) force is not magnetic and ii) motion is not
relativistic.
• Quantum mechanics approaches the problem quite differently. Here we look for a
wave function, ψ (x, t), of the particle and we get it by solving the Schrödinger
Equation
𝜕Ψ x,t ћ2 𝜕 2
• iћ = − + V x, t Ψ x, t
𝜕t 2m 𝜕x2
• The corresponding 3 dimensional equation Schrödinger Equation is
𝜕Ψ ћ2 2
• iћ = − 𝛻 Ψ + VΨ
𝜕t 2m
h
• Here, i = √-1 and ћ = = reduced Planck’s constant ≈ 1.054 x 10-34 J-s.
2𝜋
• Given suitable initial condition ψ (x, 0), we can determine ψ (x, t) for all future time,
as in classical mechanics Newton’s law determines x(t) for all future time.
• wave function, in quantum mechanics, variable quantity that mathematically
describes the wave characteristics of a particle.
• The value of the wave function of a particle at a given point of space and time is
related to the likelihood of the particle’s being there at the time.
• The wave function of a particle, at a particular time, contains all the information
that anybody at that time can have about the particle.
• But the wave function itself has no physical interpretation. It is not measurable.

• However, the square of the absolute value of the wave function has a physical
interpretation. In one dimension, we interpret |ψ(x,t)|2 as a probability density, a
probability per unit length of finding the particle at a time t at position x.
Basic postulates
1. Each particle in a physical system is described by a wave function ψ (x, y, z, t). This
𝜕Ψ 𝜕Ψ 𝜕Ψ
function and its space derivative ( + + ) are continuous, finite and single
𝜕x 𝜕y 𝜕z
valued.
• N.B.
• i) ψ is related to a physical quantity, so it can’t be discontinuous at any point.
• ii) If ψ is infinite it would imply infinite large probability of finding the particle ín
that region, which is in violation of uncertainty principle.
∞
• iii) Single valued as the function ‫׬‬−∞ Ψ ∗ Ψ 𝑑𝑥 must have only one numerical value.
2. In dealing with classical quantities such as energy E and momentum p, we must
relate these quantities with abstract quantum mechanical operators as following
Classical variables Quantum operator
• x x
• f(x) f(x)
𝜕
• p(x) - iћ
𝜕x
𝜕
• E iћ
𝜕t
• V(x) V(x)
• To every observable in classical mechanics there corresponds a linear, Hermitian
operator in quantum mechanics.
3 The statistical interpretation of the wave function
• By nature particle is localized, whereas the wave function is spread out in space.
How can such an object describe the state of a particle?
• Ψ(x, t) 2 gives the probability of finding the particle at point x at time t.
i.e.
• Ψ(x, t) 2 dx = probability of finding the particle between x and (x + dx) at time t.
• The particle would be relatively likely to be found near A, unlikely to be near B.
The shaded area represents the probability of finding the particle in the range dx.
• The wavefunction of the light wave is given by E(x,t) and its energy density is
given by E2.
• Energy of individual photon is given by E= hf and E^2 is proportional to number of
photons.
• Suppose the screen is initially unexposed to light. If the screen is exposed to very
weak light, the interference pattern appears gradually
• Individual photon hits on the screen appear as dots.

• The dot density is expected to be large at locations where the interference pattern
will be, ultimately, the most intense.

• In other words, the probability (per unit area) that a single photon will strike a
particular spot on the screen is proportional to the square of the total electric field.

• The square of the matter wave |Ψ|2 in one dimension has a similar interpretation
as the square of the electric field |E|2
• The statistical interpretation introduces a kind of indeterminacy into quantum
mechanics, i.e you can’t predict with certainty the outcome of a simple experiment
like to measure the position of a particle.

• Quantum mechanics offers statistical information about possible results.

• Is this a peculiarity of the nature, a deficiency in the theory, a fault in the

measurement apparatus, or what?

• If I measure the position of a particle and I find it to be at point C. Where was the
particle just before I made the measurement?
• The realist position: It was at C. (Einstein believed this). If this is true then
quantum mechanics is an incomplete theory since the particle was at C and
quantum mechanics was unable to tell us so. (In other words, indeterminacy is
not a fact of nature, but a reflection of our ignorance).

• God doesn’t play dice.

• The orthodox position (Copenhagen interpretation): The particle
wasn’t really anywhere. It was the act of measurement that forced
the particle to take a stand.

• The agnostic position: Refuse to answer.

• In 1964 John Bell came up with an astonishing result that it makes observable
difference if the particle had a precise (though unknown) position prior to the
measurement.

• An immediate and repeated measurement must return the same value.

• It is said that the wave function collapsed upon measurement, to a spike at the
point C (say).

• ψ, however, will soon spread in accordance with the Schrödinger equation, so the
second measurement must be made quickly.
• The Einstein–Podolsky–Rosen (EPR) paradox is a thought experiment proposed by
physicists Einstein, Podolsky and Rosen, with which they argued that the description of
physical reality provided by QM was incomplete.

• In a 1935 paper titled "Can Quantum-Mechanical Description of Physical Reality be

Considered Complete?", they argued for the existence of "elements of reality" that were
not part of quantum theory, and speculated that it should be possible to construct
a theory containing them.

•
• The thought experiment involves a pair of particles prepared in what later authors would
refer to as an entangled state.

• Einstein, Podolsky, and Rosen pointed out that, in this state, if the position of the first
particle were measured, the result of measuring the position of the second particle could
be predicted.

• If instead the momentum of the first particle were measured, then the result of
measuring the momentum of the second particle could be predicted.

• They argued that no action taken on the first particle could instantaneously affect the
other, since this would involve information being transmitted faster than light, which is
forbidden by the relativity.

•
• They invoked a principle, later known as the "EPR criterion of reality", positing
that: "If, without in any way disturbing a system, we can predict with certainty the
value of a physical quantity, then there exists an element of reality corresponding
to that quantity."

• From this, they inferred that the second particle must have a definite value of both
position and of momentum prior to either being measured.

• But in quantum mechanics these two observables are incompatible and it

therefore does not associate simultaneous values for both to any system.
Therefore, Einstein, Podolsky, and Rosen concluded that quantum theory did not
provide a complete description of reality.
• Entanglement is what Einstein referred to as "spooky action at a distance."
It's a phenomenon by which one particle can effectively "know" something
about another particle instantaneously, even if those two particles are
separated by a great distance.

• It appears to go against the idea that nothing, not even information, can
travel faster than the speed of light.

• Quantum mechanics is spooky.

• Then in 1964, the Northern Irish physicist John Stewart Bell demoted locality
from a cherished principle to a testable hypothesis.

• Bell proved that quantum mechanics predicted stronger statistical correlations in

the outcomes of certain far-apart measurements than any local theory possibly
could.

• Bell’s theorem upended one of our most deeply held intuitions about physics,
and prompted physicists to explore how quantum mechanics might enable tasks
unimaginable in a classical world.

• “The quantum revolution that’s happening now, and all these quantum
technologies — Due to Bell’s theorem,”
• EPR advocated a philosophy of science called local realism.

• This philosophy specified that interactions should not be able to communicate instantly
across large distances (nonlocally) in violation of relativity, and that systems ought to have
a "realistic" definite value of quantities before these quantities are measured.

• There must have been some extra hidden variable that set the responses of the entangled
electrons to spin measurements at the beginning of the experiment, when both electrons
were generated at the same site.

• Bell's theorem: No theory of local realism such as a local hidden variables theory can
account for the correlations between entangled electrons predicted by quantum
mechanics.
• Quantum teleportation
• It is a technique for transferring quantum information from a sender at one location
to a receiver some distance away.
• The instant transfer of ‘qubits’ (quantum bits) the basic unit of quantum
information.
• Quantum teleportation is the transfer of quantum states from one location to
another using quantum entanglement.
• Regardless of the distance, the encoded information shared by the “entangled” pair
of particles can be passed between them.
• An interesting note is that the sender knows neither the location of the recipient nor
the quantum state that will be transferred.
• Researchers are hoping to create networks of quantum computers that can share
information at blazing-fast speeds.
• But keeping this information flow stable over long distances has proven
extremely difficult due to changes in the environment including noise.
• Researchers are now hoping to scale up such a system, using both entanglement
to send information and quantum memory to store it as well.
• The Bell theorem is one of the fundamental theorems upon which relies the
widespread belief that quantum mechanics is the ultimate mathematical
framework within which the hypothetical final theory of the fundamental
building blocks of Nature and their interactions should be formulated.
• Therefore, there are two distinct physical processes, (i) the ordinary
one where wave function evolves leisurely as per Schrödinger
equation, and (ii) sudden and discontinuous collapse of the wave
function due to measurements.
Normalization of Wave function

• Since wavefunctions can in general be complex functions, the physical significance

cannot be found from the function itself.

• The physical significance is found in the product of the wavefunction and its complex
conjugate.

• Now, a probability is a real number between 0 and 1. An outcome of a measurement

which has a probability 0 is an impossible outcome, whereas an outcome which has a
probability 1 is a certain outcome.
Normalization of Wave function
2
• The product Ψ(x, t) = Ψ ∗ Ψ, Ψ ∗ being the complex conjugate of Ψ, is normalized
according to
∞ 2 ∞
‫׬‬−∞ Ψ 𝑑𝑥 = ‫׬‬−∞ Ψ ∗ Ψ 𝑑𝑥 =1

• The average or expectation value 𝛼 of any variable 𝛼 is calculated from the wave
function by using the general formula

∞
‫׬‬−∞ Ψ∗ 𝑥 𝛼Ψ(x)𝑑𝑥
• 𝛼 = ∞
‫׬‬−∞ Ψ∗ 𝑥 Ψ(x)𝑑𝑥
 ∞
• If, however, if the wave function is normalized then ‫׬‬−∞ Ψ ∗ 𝑥 Ψ x 𝑑𝑥 = 1 and
the expectation value is given by
∞
𝛼 = ‫׬‬−∞ Ψ ∗ 𝑥 𝛼 Ψ(x)𝑑𝑥

• Once we find the wave function Ψ for particle, we can calculate its average
position, energy or momentum within the limits of uncertainty principle.

• So major effort in quantum mechanics is to solve Ψ within the conditions imposed

by a particular physical system.
Formulation of Schrödinger Equation

The classical equation for energy of a particle of mass m

• Kinetic Energy + Potential Energy = Total Energy

1
• or 𝑚𝑣 2 +𝑉 =𝐸
2

𝑝2
• or +𝑉 =𝐸 where p = mv is the momentum of the particle.
2𝑚

𝜕 𝜕
• Using quantum mechanical operators for p (= - iћ ) and E (= iћ ) we get if we
𝜕x 𝜕t

allow the operators to operate on the wave function ψ(x,t)

ћ2 𝜕2 ψ(x,t) 𝜕ψ(x,t)
− + V x ψ(x, t) = iћ (1)
2m 𝜕x2 𝜕t
Eqn. 1 is the Schrödinger Equation for one dimensional problem. Here the
𝜕 𝜕2
operational interpretation of ( )2 is the second derivative form for , and i2 = -1.
𝜕x 𝜕x2

• In three dimension the Schrödinger Equation is

ћ2 2 𝜕Ψ
− 𝛻 Ψ + VΨ = iћ (2)
2m 𝜕t
• If we assume potential, V, is independent of time, t, then we can solve the
Schrödinger Equation by the method of separation of variables. We look for
solution that are simple product

Ψ x, t = ψ(x)f(t) (3)

• Using Eqn. 3 in Eqn. 1 we get

ћ2 𝜕2 ψ x 𝜕f(t)
− 𝑓(𝑡) + V x ψ(x)f(t) = iћψ(x)
2m 𝜕x2 𝜕t

• Dividing both sides by ψ(x)f(t) gives

ћ2 1 d2 ψ x 1 df(t)
− +V x = iћ (4)
2m ψ(x) dx2 f(t) dt
• Since left hand side is a function of ‘x’ only and right hand side is a function of ‘t’
alone, this is true only if both sides are separately equal to a constant. Let the
constant be E.

• Now the variables can be separated and we get time dependent Schrödinger
Equation

𝑑𝑓(𝑡) 𝑖𝐸
= − 𝑓(𝑡)
𝑑𝑡 ћ

𝑑𝑓(𝑡) 𝑖𝐸
Or + 𝑓 𝑡 =0 (5)
𝑑𝑡 ћ
• The time independent Schrödinger Equation

ћ2 1 d2 ψ x
• − +V x =E
2m ψ(x) dx2

ћ2 d2 ψ x
− + V x ψ(x) = Eψ(x) (6)
2m dx2

• Eqn. (5) and (6) are time dependent and time independent Schrödinger Equation,
respectively. Thus the separation of variables has turned a differential equation
into two ordinary differential equations.
• The general solution of Eqn. (5) is C.exp(-iEt/ћ). But we may absorb the constant
C into ψ, as our quantity of interest is ψ(x)f(t). Then
−𝑖𝐸𝑡
𝑓 𝑡 =𝑒 ћ (7)

• The Eqn. (6), known as time independent Schrödinger Equation, can be solved
when the potential V is specified.

• The general solution of Ψ x, t is

−𝑖𝐸𝑡
Ψ x, t = ψ(x)𝑒 ћ (8)
• Properties of Schrödinger's equation
• 1. Linearity: The Schrödinger equation is linear in the wave-function Ψ which
means that the equation does not involve higher powers of the wave-function or
its derivatives.
• 2. Superposition: The linearity of Schrödinger's equation implies that a linear
combination of solutions of Schrödinger's equation for any system is also a
solution. Hence, if Ψ1 and Ψ2 satisfy the Schrödinger's equation then
• Ψ = a1 Ψ1 + a2 Ψ2 (9)
is also a solution, where a1 and a2 are constants. Hence, the wave-functions Ψ1 and
Ψ2 obey the superposition principle. The superposition principle is the main
difference between quantum mechanics and classical mechanics.
• Operators, Eigenfunctions, Eigenvalues, Expectation values

• Every physical observable (quantity) in Classical Mechanics can be represented by

an operator in Quantum Mechanics which acts on the wave-function (a particular
state of the particle) to produce another wave-function. Thus,

෠ = Ψ′
• 𝑂Ψ (10)

• Where 𝑂෠ represents the operator. The following table represents the operators
associated with various observable quantities.
Observable (Quantity) Operator
Position, x x
Linear momentum, p 𝜕
−iћ
𝜕x
Potential Energy, U(x) U(x)
𝑝2 ћ2 2
Kinetic Energy, KE = − 𝛻
2𝑚
2m
Total Energy, E 𝜕Ψ
iћ
𝜕t
Hamiltonian H = KE (Kinetic Energy) + PE ћ2 2
(Potential Energy) − 𝛻 +V
2m
 ෢1 and 𝑂
• Two operators 𝑂 ෢2 are said to commute if

෢1 𝑂
•𝑂 ෢2 Ψ = 𝑂
෢2 𝑂
෢1 Ψ or ෢ ෢2 Ψ − 𝑂
𝑂1 𝑂 ෢2 𝑂
෢1 Ψ = 0 (11)

for all Ψ.

• If two operators commute, they can be simultaneously determined precisely. The

෢1 and 𝑂
commutation relation for two operators 𝑂 ෢2 is given by

• 𝑂෢ ෢ ෢෢ ෢෢
1 , 𝑂2 = 𝑂1 𝑂2 − 𝑂2 𝑂1 (12)

• If two operators commute then 𝑂෢ ෢

1 , 𝑂2 = 0
Example

Prove that the observables position x and momentum px cannot be determined

simultaneously by using the commutation relation.

Solution:

𝜕Ψ 𝜕 𝜕Ψ 𝜕Ψ 𝜕x
• 𝑥, 𝑝𝑥 Ψ = x𝑝𝑥 − 𝑝𝑥 x Ψ = −iћ x − xΨ = −iћ x − x +Ψ
𝜕x 𝜕x 𝜕x 𝜕x 𝜕x

• ∴ 𝑥, 𝑝𝑥 Ψ = iћΨ or 𝑥, 𝑝𝑥 = iћ

• Since, the operators x and px do not commute, they cannot be determined simultaneously
with 100% accuracies.
 ෠ it is possible to find a wave-function Ψ x such that
• Given an operator 𝑂,

• 𝑂෠ Ψ x = lΨ(x) (13)

• Where l is a constant independent of x. The function Ψ(x)is called an

eigenfunction of 𝑂෠ and l is the corresponding eigenvalue of 𝑂.
෠

• The observed value obtained from a single measurement is an eigenvalue.

Expectation values

• In a large number of measurements (or measurement over a prolonged period of

time), the measured value is an average value or expectation value. The
expectation value of any observable quantity a is given by

∞
‫׬‬−∞ Ψ∗ 𝑥 𝛼Ψ(x)𝑑𝑥
• 𝛼 = ∞ (14)
‫׬‬−∞ Ψ∗ 𝑥 Ψ(x)𝑑𝑥

∞
• Now, if the wave-function is normalized then ‫׬‬−∞ Ψ ∗ 𝑥 Ψ x 𝑑𝑥 = 1 and the
expectation value is given by
∞
• 𝛼 = ‫׬‬−∞ Ψ ∗ 𝑥 𝛼 Ψ(x)𝑑𝑥 (15)
• Some important properties of eigenvalues and eigenfunctions

• 1. If Ψ(x) is an eigenfunction of an operator 𝑂෠ with eigenvalue l, then bΨ(x),

where b is a constant, is also an eigenfunction of the same operator with the
same eigenvalue l. Hence, multiplying an eigenfunction with a constant does not
change the eigenvalue.

• 2. If there are two eigenfunctions having the same eigenvalue, then the
eigenfunctions are said to be degenerate eigenfunctions.

• 3. An operator is termed as a Hermitian operator if all its eigenvalues are real and
the eigenfunctions corresponding to different eigenvalues are orthogonal.
Example

• A particle limited to the x axis has wave-function Ψ = ax between x = 0 and x = 1;

while Ψ = 0 elsewhere, (a) Find the probability that the particle can be found
between x = 0.45 and x = 0.55, (b) Find the expectation value of the particle's
position.

Solution:
Example 4

• An eigenfunction of the operator d2/dx2 is Ψ = e2x. Find the corresponding

eigenvalue.

Solution:

𝑑2 𝑑2 2x
• Let 𝑂෠ = , ෠ =
so, 𝑂Ψ e 2x
= 4e = 4Ψ
𝑑𝑥 2 𝑑𝑥 2

• Comparing it with the Eq. 𝑂෠ Ψ x = lΨ(x) , we obtain l = 4.

• Hence, the eigenvalue of the given operator is 4.

Schrödinger's equation : Time-Dependent Form for a free particle
• The one-dimensional time dependent Schrödinger equation for a free non-
relativistic particle (V = 0) is given below
ћ2 𝜕2 ψ(x,t) 𝜕ψ(x,t)
• − = iћ (1)
2m 𝜕x2 𝜕t
• A free particle of total energy E and momentum p moving in the +x direction can
be described by the wave-function Ψ of a monochromatic wave. The expression
for Ψ is given by
i
• Ψ x, t = A exp (px − Et) (2)
ћ
• where A = amplitude of displacement of the wave
• ћ = reduced Planck constant (h/2pi) = 1.05457 x 10-34 J.s
• If we use the “guess-and-check” method to solve for a solution ψx to this
differential equation, we’ll see that there are many different solutions.
• The energy E and momentum p of the particle are related to its wave-
vector k and frequency w by the relations

2𝜋
• p = ћk = ћ , E = ћw
𝑙

• Differentiating Eq. (2) once with respect to time gives,

𝜕Ψ(x,t) 𝐸
• = −𝑖 Ψ x, t
𝜕𝑡 ћ

• or
𝜕Ψ(x,t)
iћ = EΨ x, t (3)
𝜕t
• Differentiating Eq. (2) twice with respect to x gives,

𝜕Ψ x,t
• −iћ = pΨ x, t
𝜕x

2 𝜕2 Ψ x,t
• −ћ = p2 Ψ x, t (4)
𝜕x2

• Dividing both sides of Eq. (4) by (1/2m), we obtain,

ћ2 𝜕2 Ψ x,t p2
− = Ψ x, t (5)
2m 𝜕x2 2m
 ћ2 𝜕2 ψ(x,t) 𝜕ψ(x,t)
• − = iћ (1)
2m 𝜕x2 𝜕t

𝜕Ψ(x,t)
• iћ = EΨ x, t (3)
𝜕t

ћ2 𝜕2 Ψ x,t p2
• − = Ψ x, t (5)
2m 𝜕x2 2m

• Comparing equations (1), (3) and (5), the energy E and momentum p of a free

non-relativistic particle of mass m are related by the expression

𝑝2 ℏ2 𝑘 2
• 𝐸= = (6)
2𝑚 2𝑚
• As the particle is free, there are no boundary conditions to be applied
to the particle motion and hence there are no restrictions on wave-
vector k.
• As a result, the particle can possess any value of energy or the energy
is not quantized.
• Thus, a freely moving particle possesses a continuous energy.
Calculate the normalization constant for a wave function given by (at t = 0)
• 𝜓 𝑥 = 𝐴𝑒𝑥𝑝(−𝜎 2 𝑥 2 /2)exp(𝑖𝑘𝑥) [A= (σ/√π)1/2]
• Find the dimensions of a i) 3-dimensional wave function and ii) 1-
dimensional wave function.
• Which among the following represent a well behaved wave function?
a. ψ = x^2 , b. ψ = 2e^x , c. 𝜓 = 𝐴𝑒^−𝑥^2
 V=∞
Some applications of Schrödinger's equation V=∞

• Infinite Square-well Potential

• Let us solve the problem of infinite potential well.

V=0

• Let us assume that a particle of mass m trapped in a

x=0 x=L

• one-dimensional infinitely deep potential well with

• V(x) = 0 except at boundaries x=0 and x=L, where it is infinitely large as shown in the figure.

• Therefore,

• V(x) = 0 for 0 < x < L

• = ∞ for x ≤ 0 and x ≥ L (1)

• We have to find out the eigenfunction and the corresponding eigenvalues for this problem.
• Inside the well V(x) = 0. Therefore, the time independent Schrödinger
equation can be written as
d2 y x 2mE
• + y x =0 0<x<L (2)
dx2 ћ2

d2 y x
• + k2y x = 0 (3)
dx2
2mE
• Where k2 =
ћ2
This is simple harmonic oscillator equation. The general solution is

• y x = A sinkx + B cos kx (4)

• Where A and B are the arbitrary constants that can be found from boundary conditions.

• Continuity of ψ(x) requires

• ψ(0) = ψ(L) = 0 (5)

• y 0 = A sin k. 0 + B cos(k . 0) = 0

• Therefore, 𝐵=0

• and y x = A sin(kx) (6)

• Now y L = Asin(kL) = 0
• Since A cannot be zero as it will give trivial, non normalizable solution
ψ(x) = 0, we have

• sin (kL) = 0 or kL = 0, ±π, ±2 π, ±3 π, ….

• Again k=0 is not acceptable as it will imply ψ(x) = 0 and the ‘-’ve sign can
be absorbed into A. Therefore we have
𝑛𝜋
• 𝑘𝑛 = n = 1, 2, 3, ...... (7)
𝐿
 2mE 𝑛𝜋
• k2 = , 𝑘𝑛 =
ћ2 𝐿

• From Eqn. (3) and (7), we solve for the total energy En for each value of the integer n

√(2𝑚𝐸𝑛 ) 𝑛π π2 𝑛 2 ћ 2
• = 𝐸𝑛 =
ћ 𝐿 2𝑚𝐿2

(8)

• In contrast to the classical case, a quantum particle in the infinite square well can have only

certain, discrete values of energy depending on the value of n.

• Thus, the energy becomes quantized due to confinement of the particle. Hence, a particle

in an infinite potential well can have only bound states.

• The energy E1 is called the zero-point energy. Obviously, the energy is not zero in
this case.

• The zero-point energy is the consequence of the uncertainty principle.

• If the energy of the particle is zero, its momentum is also zero.

• Then according to uncertainty principle, the position of the particle would

become infinite and the particle cannot be confined to the box. Therefore, the
particle cannot have zero energy.
• The eigenfunctions corresponding to the above energy eigenvalues is given by

2𝑚𝐸𝑛
• y𝑛 = 𝐴 sin 𝑘𝑥 = 𝐴 sin 𝑥 (9)
ћ2

• The constant A can be found from the normalization condition,

𝐿 𝐿 𝑛𝜋𝑥 𝐿
• ‫׬‬0 y𝑛 2 𝑑𝑥 = 𝐴2 ‫׬‬0 𝑠𝑖𝑛2 𝑑𝑥 = 𝐴2 = 1
𝐿 2

2
• Or 𝐴= (10)
𝐿
• Hence, the normalized wave-functions for a particle in a one-dimensional infinitely
deep potential well is given by
2 𝑛𝜋𝑥
• y𝑛 𝑥 = 𝑠𝑖𝑛 where n = 1, 2, 3, ……. (11)
𝐿 𝐿

• First three wave functions are shown above.

•