Fundamentals of Chemistry
(CHEM F101)
Semester I, 2025-26
Lecture-2
07/08/2025
Well behaved wavefunction for a physical system
Four conditions are put forward to make probability functions,
which are solution of Schrödinger equations, consistent with
a reasonable picture of nature.
• Ψ must be single-valued.
• Ψ must be finite everywhere.
• Ψ must be continuous.
• !ψ/!" must be continuous.
Normalization of wavefunction
is a consequence of Born
Interpretation.
An unacceptable wavefunction:
(a) is not single-valued
(b) is infinite over a finite coordinate range
(c) is not continuous
(d) slope is not continuous.
Boundary condition
Wave function should
vanish at the boundaries
Acceptable
Well- behaved
Boundary condition Wave function should
vanish at the boundaries
Boundary conditions: Acceptable wavefunctions
Boundary conditions to
be satisfied by the
wavefunctions
The fact that only some solutions are acceptable, together with the fact
that each solution corresponds to a characteristic value of E, implies that
only certain values of energy are acceptable. That is when Schrodinger
eqn is solved subject to the boundary conditions that the solution must
satisfy, we find that the energy of system is quantized.
Planck and his successors postulated the quantization of energy for
each system they considered. But, now quantization is an automatic
feature of a single equation, the Schrodinger eqn., which is
applicable to all systems.
Normalization
Ø Thus wavefunctions need to be normalized
Ø Wavefunctions are normalized if and only if
+"
! $ $ =
*
dx 1
#"
Consider y(x) = sin(2πx) with 0 ≤ x ≤1, probability
would be
1 1
P(x) = 0ò y2 dx = 0ò sin2(2px) dx = 1/2
In order for the particle to exist in the given
region of space, the probability P(x) should be 1
and not 1/2.
In order to have 100% probability,
1
we need to multiply the
wavefunction with a constant, then y(x) = A sin(2πx)
P(x) = A2 0ò y2 dx = A2 0ò sin2(2px) dx = 1, A = √2,
Normalization constant
ØUsually the wave function is multiplied with a constant so
that normalization condition can be satisfied
ØIt doesn’t affect the shape of the function, it only imposes
a scaling factor on the amplitude
Simply means that we are multiplying the wavefunction by a
constant to ensure that the sum of the probabilities = 1.
(Integral limits would be modified to represent the limits of space a particle exhibits)
8
Operators
For every observable in classical mechanics, there is a
corresponding operator in quantum mechanics.
Observables in Quantum mechanics: Each dynamical variable
! and its expectation value in a
is associated to a linear operator ",
quantum state can be computed. Apply the operator on the state
function of the systems – outcome will be the observable.
Operators and eigen value equation
Schrodinger eqn is an eigen value equation
! = %#
"#
! eigen function: ψ, eigen value: %
Operator: ",
Example:
dx
(
d ax
e ) = a (e )
ax
d/dx (operator) acting on eax (eigen function)
giving eigen value = a
Eigen value equation
Operator on function = constant × function
Observables : position, momentum, K.E, P.E etc.
ℏ' )'
! $
Operators : ", !" , − * (")
,+
'( )"'
Eigen values must be real numbers
Hamiltonian, the total energy operator
Hamiltonian Operator, Ĥ
Operator corresponding to the Total energy
Total energy = KE + PE
p2
E = + V ( x, t )
2m
Ĥ - Operator for Total energy, E, of the system
2
Px Classical energy for a
E = + V ( x) Particle in one dimension
2m
1. Which of the following are eigen functions of d2/dx2 ? Find the
corresponding eigen values.
y = 8e4x y = cos(x/4) y = kx2
= 16 x (8e4x) = -1/16 x (cos(x/4)) Not an eigen function
2. Is eax is an eigen function of operator dn/dxn ? What is the eigen value?
Yes. The eigen value is an
An
eigenfunction, in the context of linear algebra and functional analysis
, is a non-zero function that, when acted upon by a specific linear
operator, produces a scalar multiple of itself.
Quantum Mechanics: Schrodinger Equation
Different steps to construct the Schrödinger equation
1. Write the classical mechanical expression for total energy
2. Total energy = K.E + P.E
3. For a particle of mass m in one dimensions
1 (
2
E = mv x + V ( x) "
!# = −&ℏ
2 ()
2
Px ℏ* - *
E= + V ( x)
2m Kinetic Energy operator = −
+, -# *
operators px ,py, pz etc. should be replaced with
2 2
! d
H =! + V ( x)
2m dx 2
Wavefunction and energy from the Schrodinger Equation
Ø Wave functions are solutions of the Schrödinger
equation
Ø Time independent Schrödinger equation is a linear 2nd
order differential equation: to get the general solution,
we need the ‘boundary conditions’
Ø If there are two boundary conditions: we get two
equations to solve à We get values for the two
unknowns (y & E)
Quantum Mechanics: Schrodinger Equation
The wavefunction y satisfies the Schrodinger equation
Ĥψ=Eψ
where Ĥ is called the Hamiltonian operator, a set of well
defined operations to be carried out on the function ψ, and
represents the energy. In one dimension, the Hamiltonian
may be written as
Ĥ = (-ħ2/2m) d2/dx2 + V(x)
where V(x) is the potential energy to which the particle is subjected.
Second order linear partial differential equation of motion
(the time independent form)
Schrodinger Equation
The Schrodinger equation for a microscopic
particle of mass m moving in one dimension may
thus be written as
ℏ# %#
− ['(&)] + ,(&)'(&) = .'(&)
#$ %&#
where E is the total energy of the system.
In three dimensions,
ℏ# /# /# /#
− + + ['(&, 0, 1)] +
#$ %&# %0# %1#
,(&, 0, 1)'(&, 0, 1) = .'(&, 0, 1)
Solutions to the time-independent
Schrodinger equation for some simple
systems
Free particle in one dimension
-(ħ2/2m) d2y(x)/dx2 = Ey(x)
y(x) = sin(kx) [one of the solutions]
where k = (2mE)1/2/ħ, E = ħ2k2/2m
But for a free particle, E = p2/2m = ħ2k2/2m
or p = ħk
Now, sin(kx) is a wave of wavelength l = 2p/k. Putting
the two together, we find
l = h/p, the de Broglie relation.
The eigenfunction eikx for k >0 represents the particle moving from
left to right on the x-axis (blue curve in below Figure) with
momentum p > 0. Correspondingly, e-ikx represents motion from right
to left with p < 0.
Figure: Two waves traveling in opposite directions across the same medium
combine linearly. In this animation, both waves are of the same wavelength
and the sum of amplitudes results in a standing wave.
Particle in a box – (Quantized) Translation
Consider a particle in one dimension confined to a
length L by infinite potential barriers at x = 0 and x =
L (infinitely deep potential well)
V=¥ V=¥
V=¥ V=¥
V=0 V=0
y=0 y=0
inside box inside box
y = 0, implies particle does not exist there V V
Region I Region II Region III
V= 0
! d!2 2 V= ! V= !
" 2
= E!
2m dx X=0 X=l
For x < 0 and x > L, y = 0 since probability of
finding the particle in these regions is zero.
For 0 £ x £ L, the solution to the Schrodinger
equation is
y(x) = N sin(kx) + M cos(kx)
with k = (2mE) /ħ
1/2
y(x) = N sin(kx) + M cos(kx)
Boundary Conditions – Quantization
Acceptable wavefunctions – must be continuous, (also
finite and single valued). In this case then,
y must equal 0 at x = 0, and at x = L. The first is satisfied
setting M = 0. For the second, need
kL = np, n = 1,2,3,…..
‘n’ is a quantum number
En = n2h2/8mL2 : Quantized energy levels!
yn = N sin(npx/L) : Wavefunctions corresponding to the
energy levels.
‘N’ is the normalization constant. (Wavefunctions
must be normalizable).
0ò L y 2 dx = N2 ò L sin2(npx/L) dx = 1 (Why?)
n 0
ÞN2L/2 = 1
or N = (2/L)½
The normalized wavefunctions are therefore
yn = (2/L)½ sin(npx/L) , n = 1,2,3,…..
