Attention: Students of
Section 4 (Chemistry I)
The venue of tutorial class has
been changed from Room No.
2237 to Room No. 3246 from
the next class (Monday, August
16, 2010 onwards).
What we have studied in the previous lecture?
Recognized that classical theory is inadequate
Inadequacy exhibited by properties of Black body
radiation
Inadequacy exhibited by features of Photoelectric effect
In the process of understanding quantum hypothesis is
invoked
Some of the major features/equations/highlights:
Wiens Law; maxT = Constant
Stefan-Boltzmann Law: Emittance = T4
Planck: ()d
hc/
5)(ehc/kT - 1)-1 d
() = (8
Quantum phenomena: E = nh
Photoelectric effect: Ek = h
= h(
0)
Line Spectra
Hot gas emits radiations with the characteristic wavelengths
corresponding to the transitions between different energy
levels of the atoms or molecules in the gas. This leads to
bright lines in the spectrum.
A hot source emits continuous radiation and a cool gas in the
way absorbs radiations with the characteristic wavelengths
corresponding to the transitions between different energy
levels of the atoms or molecules in the gas.
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 atom:
= 1/
= RH(1/n12 1/n22)
where RH = 109677 cm-1 is the Rydberg constant for H,
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
Electron of mass m, moves in a circular orbit of radius
r, about stationary nucleus of mass M, charge Ze
Electrons are held by force needed to move an object
in a circle at constant speed (centripetal force)
mv2/r = Ze2/40r2 (Coulomb force)
Bohr model of hydrogen-like atom
To account for the line spectrum, Bohr proposed
stable orbits (or energy levels), for the electron,
given by the quantization condition for angular
momentum
mvr = nh/2
= n, n = 1,2,3,.
Orbiting electrons possess discrete energies - Not
every orbit is possible but only certain specific
ones.
A semiclassical model
Bohr model of hydrogen-like atom
mv2/r = Ze2/4
0r2 (Coulomb force)
Bohr assumption: mvr = n
r = 4
0n22/mZe2
Potential energy V(r) = -Ze2/4
0r
The Bohr radius a0 = 4
02/me2
Potential energy V(r) = -Z2e2/4
0a0n2
Bohr model of hydrogen-like atom
Kinetic energy:
K = mv2 = p2/2m = n22/2mr2
K = mZ2e4/32
202n22 = Z2e2/8
0a0n2
Combine kinetic and potential energy to get the total
energy
Total Energy E = K + V = -Z2e2/8
0a0n2
RH = me4/32
2c023=me4/8c02h3
Virial theorem obeyed: 2K = nV for V = rn
Bohr model of hydrogen-like atom
The laws of classical mechanics do not apply
when an electron makes a jump.
When an electron makes a jump from one orbit
to another the energy difference is carried off (or
supplied) by a photon which has an energy equal
to the energy difference between the two orbitals.
Bohr model of hydrogen-like atom
For the hydrogen atom, one obtains
En = hcRH/n2
= 1/
= RH(1/n12 1/n22)
which is the experimentally observed result.
This accounts for the spectrum. (While this
expression for the energy levels is correct, the Bohr
model is fundamentally incorrect)
Bohr model of hydrogen-like atom
A few limitations Bohr model had
The spectra of larger atoms. At best, it can make
some approximate predictions about the emission
spectra for atoms with a single outer-shell electron
The relative intensities of spectral lines
The existence of hyperfine structure in spectral
lines.
The Zeeman effect - changes in spectral lines due to
external magnetic fields
Invalid Assumptions of Classical Physics
1. Any type of motion can be excited to a state of
arbitrary energy: Oscillation of a pendulum
A strange duality! Wave or Particle!
Wave-Particle Duality
Particles: mass, momentum, angular momentum,
etc. and collision, attraction/repulsion, etc.
Waves: wavelength, amplitude, frequency, etc.
and diffraction, interference, etc.
Diffraction: Bending,
spreading and
interference of waves
passing thro gap
Interference: Superposition of two or
more waves to generate new patterns
Constructive; destructive
Electron Diffraction
Firing electron at an object and observing the
scattering (analogous: X-ray and neutron
diffraction): Davisson and Germer 1925
Investigation of the angular distribution of electrons scattered
from nickel: electron beam was scattered by the surface atoms
at the exact angles predicted for the diffraction of waves, with a
typical wavelength =1.228/V nm
A strange duality: electrons, photons .!!!
Corpuscular as well as wave like!!!!!!
Louis-Victor-Pierre-Raymond, 7th duc de Broglie
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 de Broglie
wave lengths are immeasurably small.
How much large objects
wave manifestation is
observable and known?
C60 fullerenes wave manifestation:
Large, massive object
(diameter is in nanometer range)
de Broglie wavelength is 2.5 pm i.e. about 400 times smaller
than diameter.
Largest object for which quantum-mechanical wave-like
properties have been directly observed in diffraction.
Journal: Nature 401: 680-682, 1999
Invalid Assumptions of Classical Physics
2. Waves and Particles are distinct concepts.
These are excellent assumptions at the
macroscopic level, but break down when one
considers the microscopic level:
Behaviour of very small entities such as electrons,
atoms, molecules, etc.
An Uncertainty or Indeterminacy!
An Uncertainty or Indeterminacy!
Consider in a time-varying sound wave
It is meaningless to ask about the frequency
spectrum at a single moment in time.
Why? - because the measure of frequency is the measure
of a repetition recurring over a period of time.
In order to determine the frequencies accurately,
the sound signal needs to be sampled for a finite
(non zero) time.
Time precision is lost in favor of a more accurate
measurement of the frequency spectrum
An Uncertainty or Indeterminacy!
Longer a musical note sustains, better is the
accuracy with which one can measure the
frequency..... frequency of a short-lasting sound
can not be measured accurately.
A property of Conjugate variables :
share an uncertainty relation
Time and Energy
Position and Momentum
The more
precisely the
position is
known
the less
precisely the
momentum is
known
in this instant,
Uncertainty or
indeterminacy
-Heisenberg
and vice
versa
-Heisenberg
copyright 1998 - 2006 American Institute of Physics
Heisenberg Uncertainty Principle
It is impossible to specify simultaneously, with
arbitrary precision, (a given Cartesian component
of) the momentum and position of a particle. The
product of the uncertainties in their simultaneous
measurements is greater than or equal to /2.
px x /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.
Uncertainty Principle
Definite wavelength Definite momentum but
since wave is spread out everywhere, no
information about position.
Wavefunction for particle with precisely defined
position
A sharply localized wavefunction can be generated
by adding/superposition of large/infinite number
of wavefunctions
Superposition of many waves corresponds to
superpositon of many different linear momenta (de
Broglie) momentum information is blurred
You can get localization of particle only at the
expense of/loss of precise information about the
momenta
Invalid Assumptions of Classical Physics
3. Particle travels in a trajectory or a path, with a
precise position and momentum at each instant.
Deterministic to Probabilistic
World!
Assuring words!
No serious observable to macroscopic world
Quantum mechanical wave carries the information
about particle position and momentum and also
any other observable that can be derived from
position and momentum.
Wave expresses information and can be used as a
mathematical model.
Deterministic to Probabilistic
World!
A quantum mechanical wave in its most salient
and simple form is a solution to a differential
equation
Partial differential equations can describe waves:
light wave, sound wave, water waves).
Uncertainty Principle
Consequence: Behavior of light and matter for
example, can be described by a differential
equation in terms of WAVE FUNCTION
Such wave function should give the probability of
finding the particle at a point correctly
Wave functions are themselves neither an
observable neither measurable.
Note, the probability of a particle being in any location is
described by wave function (diffraction, interference), but
the actual real, physical appearance is that of a particle
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.
