General Chemistry

(CHEM F111)

Lecture-2
16/01/2024
(F103)
Recap

Black body radiation

Rayleigh-Jeans law
Planck’s theory
Photo-electric effect
 Major experimental observations black body radiation
➢Not all wavelengths are
emitted equally
➢At any temperature, the
intensity of emitted
light → 0 as the
wavelength → 0
➢It increases to some
maximum intensity Imax
at some wavelength max
•max : wavelength of the
radiation with greatest
contribution to energy density
 Explanation (EINSTEIN 1905)
1. Light of frequency  may be considered as a
collection of particles, called photons, each of
energy h.
2. If the minimum energy required to remove an
electron from the metal surface is  (work
function), then if h < , no emission of
electrons occurs.
3. Threshold frequency 0 given by  = h0
4. For  > 0, the kinetic energy of the emitted
electron Ek = h −  = h( − 0).
 Equations

• maxT = 2.9 mm K (constant)

• M = aT4 where ‘a’ =56.7 x 10-9 Wm-2K-4
• ()d = (8π kT/ 4) d
• ()d = (hc/)(ehc/kT - 1)-1(8/4)d
• Ek = h −  = h( − 0).
Today’s topic

1. Line-spectra of H-atom
2. Electron-diffraction
3. Wave-particle duality
4. Two-slit experiment
5. Heisenberg Uncertainty principle
Line Spectrum of Hydrogen atom
Transitions between quantized energy levels of atom or
molecule, with absorption or emission of photon accounts
for line spectra.
The frequencies (in wave numbers) at which the
lines occur in the spectrum of hydrogen are given
by the formula
= 1/ = RH(1/n12 − 1/n22)
where RH = 109677 cm-1 is the Rydberg constant, n1
and n2 > n1 are positive integers, the various series
corresponding to Lyman (n1 = 1), Balmer (n1 = 2),
Paschen (n1 = 3), Brackett (n1 = 4), Pfund (n1 = 5).
 Electron Diffraction

Davisson, Germer and G P Thomson 1925

Louis de Broglie Erwin Schrodinger
 Wave-Particle Duality
de Broglie: Just as light exhibits both ‘wave-like’
(diffraction), and ‘particle-like’ characteristics, so should
all material objects.
For light (photon) E = pc = hc/
 p = h/
de Broglie (1924) suggested that this is more generally true
of all material objects. A particle moving with linear
momentum p, has an associated ‘matter-wave’ of wave
length
 = h/p
Macroscopic objects are so massive that the de
Broglie wave lengths are immeasurably small.
Wave – particle duality : Some two-
slit experiments
Experiment with Bullets:
Arrive in identical discrete lumps – particles
Distribution with both slits open is the sum of that
with slit 1 alone open and that with slit 2 alone
open – No interference.
Experiment with water waves:
Intensity can be varied by changing amplitude of
source (Intensity proportional to square of
amplitude) – no lumps.
Intensities don’t add, the amplitudes do – there is
interference - waves
 Two-slit experiment with microscopic particle like
electrons/photons etc.

Arrive in identical lumps – particles, but

distribution shows interference – wave behaviour.
❑ System has a dual potential nature, but the observed
nature is particle-like or wave-like, depending on the
nature of the observation.
❑ Interference pattern observed even if electrons/photons
sent one at a time, so in a sense each electron/photon
interferes with itself– Position not sharply defined until
it is actually observed.
❑ If the experiment capable of determining which
alternative is taken, the particle attribute, then the
interference, manifestation of the wave attribute is lost.
❑ Does the experiment with bullets show interference?
Yes, but not seen due to the scale.
 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 position and momentum of a particle.
x px  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.
Operators
For every observable in classical mechanics, there
is a corresponding operator in quantum mechanics.
Observables in Quantum mechanics: Apply the operator on
the state function of the systems – outcome will be observable.
Operators and eigen value equation
Schrodinger eqn is an eigen value eqn.:
Ĥψ=Eψ
Operator: Ĥ, eigen function: ψ, eigen value: E
Example:
dx
(
d ax
e ) = a(e )
ax

d/dx (operator) acting on eax (eigen function)

giving eigen value = a
 Schrodinger equation
The Schrodinger equation for a microscopic
particle of mass m moving in one dimension may
thus be written as
−(ħ2/2m) d2ψ(x)/dx2 + V(x)ψ(x) = Eψ(x)
where E is the energy.
In three dimensions,
−(ħ2/2m) (2 ψ/x2 + 2 ψ/y2 + 2ψ/z2) +
V(x,y,z)ψ(x,y,z) = Eψ(x,y,z)
Well behaved wavefunction for a physical system
Four conditions are put forward to make probability functions,
which are solution of Schröndinger equations, consistent with
a reasonable picture of nature.

• Ψ must be single-valued.
• Ψ must be finite everywhere.
• Ψ must be continuous.
• 𝑑ψ/𝑑𝑥 must be continuous.
Normalization of wavefunction
is a consequence of Born
Interpretation.
An unacceptable wavefunction because
(a) it is not single-valued,
(b) it is infinite over a finite range,
(c) it is not continuous,
(d) its slope is not continuous.