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Lecture 2

The lecture covers fundamental concepts in general chemistry, including Wien’s Law, Stefan-Boltzmann Law, and Planck's formula, as well as the photoelectric effect and its observations. It discusses the wave-particle duality of light and matter, the implications of de Broglie's hypothesis, and the uncertainty principle in quantum mechanics. The lecture also touches on the hydrogen atom's line spectrum and the Bohr model, emphasizing the transition between classical and quantum mechanics.

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6 views25 pages

Lecture 2

The lecture covers fundamental concepts in general chemistry, including Wien’s Law, Stefan-Boltzmann Law, and Planck's formula, as well as the photoelectric effect and its observations. It discusses the wave-particle duality of light and matter, the implications of de Broglie's hypothesis, and the uncertainty principle in quantum mechanics. The lecture also touches on the hydrogen atom's line spectrum and the Bohr model, emphasizing the transition between classical and quantum mechanics.

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BITS Pilani

Pilani Campus

CHEM F111 : General


Chemistry
Semester I: AY 2020-21
Lecture-02, 06-11-2020
Summary: Lecture -
01

m
ax

• Wien’s Law: maxT = 2.99 mm K (Constant)


• Stefan-Boltzman Law: M = aT4
• Rayleigh-Jeans: d = (8kT/4)d
• Planck’s Formula:
d = (hc/)(ehc/kT - 1)-1(8/4)d
Extension of Planck’s
formula

Planck
Einstein
Photoelectric effect (1886-
1887)

Emission of electrons from metals when


exposed to (ultraviolet) radiation.
Photoelectric effect-
Observations
1. No emission of electrons if the frequency of
radiation is below a threshold value
characteristic of the metal, however high the
intensity of the light.
2. Kinetic energy of emitted electrons varies
linearly with the frequency of the incident
radiation, and is independent of light intensity.
3. For frequencies above the threshold value,
emission of electrons is instantaneous, no
matter how low the intensity of the light.
Photoelectric effect - Classical
Theory
electronse e

e
light

metal

Light wave “hits” electron gently.


Low Intensity Electrons come out – low speed.

High Intensity
Light wave “hits” electron hard.
Electrons come out – high speed.
Non-classical Explanation,
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)
Explanation: Einstein, 1905

Work out: When Li is irradiated with light, one finds a stopping


potential of 1.83 V for =3000 Å and 0.80 V for =4000 Å.
Calculate (a) Planck’s constant, (b) the threshold potential, and (c)
the work function of Li.
Line Spectrum of Hydrogen atom
Line Spectrum of Hydrogen atom

Transitions between quantized


energy levels of atom or
molecule, with absorption or
emission of photon accounts
for line spectra.
Line Spectrum of Hydrogen atom
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).
Bohr model of hydrogen like atom: Bohr proposed stable
orbits for the electron, given by the quantization for
angular momentum
mvr = nh/2 = nħ, n = 1,2,3,….
Electron mass should be replaced by reduced mass in the
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.
Two slit experiments

Experiment with water waves:


Intensity can be varied by changing amplitude of source –
no lumps.
Clear indication of interference - waves
Two slit experiments

Experiment with electrons/photons etc. :


Arrive in identical lumps – particles, but distribution
shows interference – wave behavior.
Electron Diffraction

(Detect
or)

Davisson and Germer 1925


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
Wave-Particle Duality

Macroscopic objects are so massive that the de Broglie


wave lengths are immeasurably small.
Wave-Particle Duality:
Consequences
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.
Only the probabilities of particular results can be
predicted, and these are the squares of probability
amplitudes, or ‘wavefunctions’.
Does the experiment with bullets show interference? Yes,
but not seen due to the scale.
Matter wave
Matter wave
Wave length associated with the particle having a
momentum p is,

We’ll finally
obtain:

….Equn
.1
Equation of state for a particle of mass m moving in a potential
field of u(x)
State in classical- & quantum-
mechanics
Macroscopic objects:
• Specification of the positon and momenta of each
particle of the system at a particular time.
• Specification of the forces acting on the particles.
Microscopic particles:
• We can not determine simultaneously the exact
positon and momenta of a microscopic particle
(px x  ħ/2)
Information required in classical mechanics to
predict the future motion of a particle can not be
obtained.
Uncertainty Principle

Definite wavelength 
Definite momentum.
Since wave is spread out
everywhere, no information
about position.
Uncertainty Principle

Superposition of waves
of definite wavelength
to yield a localized
wavefunction –
momentum not
precisely defined.
Approach to quantum
mechanics
• Postulate the basic principles.
• Use those postulates and/or experimental observation.
• Propose a function – state or wave function (ψ).
• In general, ψ is a function of space (x, in 1D) and time (t)
ψ ≡ ψ (x, t)
• Wave function contains all the information about a
system.
Interested in stationary states: ψ(x)
• Schröndinger equation of mass m – rearrange Equn. 1:
Summary

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