General Chemistry (CHEM

F111)

Lecture-3
16/01/2024
Recap
1. Photo-electric effect
2. Line-spectra of H-atom
3. Electron-diffraction
4. Wave-particle duality
5. Two-slit experiment
Today’s topic
1. Heisenberg Uncertainty principle
2.Wavefunction, Born interpretation and
stationary state
3. Schrodinger eqn. (Eqn. for de Broglie
wave)
 Uncertainty Principle

Definite wavelength Definite momentum but since wave

is spread out everywhere, no information about position.
Wavefunction for particle with precisely defined
position
Superposition of waves of definite wavelength to yield a
localized wavefunction – momentum not precisely defined.
 Heisenberg Uncertainty Principle
It is impossible to specify simultaneously, with
arbitrary precision, (a given Cartesian component
of) the momentum and position of a particle.
px x  ħ/2
•Complementary variables, increase in the
precision of one possible only at the cost of a loss of
precision in the other.
•Trajectories not defined precisely.
 Invalid Assumptions of Classical
Physics
1. Particle travels in a trajectory or path, with a precise
position and momentum at each instant.
2. Any type of motion can be excited to a state of arbitrary
energy.
3. ‘Waves’ and ‘Particles’ are distinct concepts.

These are excellent assumptions at the macroscopic level,

but break down when one considers the behaviour of very
small entities such as electrons, atoms, molecules, etc.
 WAVEFUNCTION / (PSI)

In classical mechanics, a particle may have a well-defined trajectory,

with a precisely specified position and momentum at each instant.

According to quantum mechanics, a particle cannot have a precise

trajectory; instead, there is only a probability that it may be found
at a specific location at any instant.

The wavefunction that determines its probability distribution is a

kind of blurred version of the trajectory. Here, the wavefunction is
represented by areas of shading: the darker the area, the greater
the probability of finding the particle there.
 WAVEFUNCTION / (PSI)
The state of a system (particle) is completely specified by
its wavefunction (x,y,z,t), which is a probability
amplitude and has the significance that

2 dV

(more generally 2dV since  may be complex)

represents the probability that the particle is located in the
infinitesimal element of volume dV about the given point,
at time t.
(Born interpretation of wavefunction)
 Time Evolution or Dynamics

The dynamics or time-variation of a general

quantum mechanical system is described by the
variation in  with time, ie., through an equation
for t, and not in terms of a precisely defined
trajectory or path.
 Stationary States
In many situations of interest in chemistry, one is
concerned with stationary states, in which the
probability distribution is independent of time. The
part of  which depends on t is simple in such
states, and factors out.
For such states,
ψ2 dV
represents the (time-independent) probability
distribution, where the wavefunction ψ(x,y,z) is a
function of the spatial coordinates alone.
2 is physically significant
 Schrodinger Equation
(An equation for de Broglie’s
matter wave)
The wavefunction  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.