Chem.

266
Physical Chemistry III
Quantum Chemistry

Instructor: Dr. Joel R. Salazar

Office: Dept. of Chemistry, CAS, CLSU
E-mail: chemistjoel2004 @yahoo.com
ConsultationHours: Monday to Thursday
 The Course

Prerequisite
• Tools from elementary calculus and differential
equations
Resources
• Physical Chemistry
By : P.W.Atkins, Alberty, Levine, Ball, Laidler, Castillan
Physical Chemistry : A Molecular Approach
By. D. Mc Quarrie
• Lectures
(principles, procedures, interpretation, tricks, insight)

• Homework problems and solutions

Course Planner

o Material covered in lectures. What to focus on or review.

o What to study from the book.
o Homework assignments.
o Questions for further thinking.
 Development of
Quantum Mechanics
Chem. 260 Lecture Notes
Quantum Mechanics and
Quantum Chemistry
 Quantum Mechanics
Laws governing the behavior of very small
particles
 Determines the properties of nanomaterials
(1 to 100 nm)
 Quantum Chemistry
 Application of quantum mechanics to
problems in chemistry
Electronic Structure of Atom
 From studies of the properties of light or
radiant energy also called
electromagnetic radiation.
Nature of the Electromagnetic Radiation
 All radiant energy has wavelike
characteristics ( analogous to those of
waves that move through water)

 Properties of any kind of wave

i.) wavelength (λ) ii.) frequency (ν)
iii.) velocity iv.) amplitude
 Properties of any kind of wave
1.) wavelength = the distance between two
neighboring crests or through of a wave
= measured in terms of nm
2.) frequency = number of waves/second
= represented as cycles /second
or Hertz (Hz)
3.) velocity = distance traveled by the wave in
one second
c=νxλ
4.) amplitude = height of a crest or depth of the trough
Important Notes
 Determination of the λ or frequency of radiation
is done by means of a devise known as “
spectrometer”.
 All electromagnetic radiation travel with the same
velocity and may differ in their wavelength and
frequency.
 The velocity of an electromagnetic wave (light) is
found to be constant and independent of the
medium in which the wave travels
(electromagnetic waves do not require any
medium of propagation)
Origins of Quantum Theory
Radiation acts as discrete packets of energy
called “quanta”.

1885- 1908: Atomic spectra (Line spectrum of H

gas is an emission spectrum)

Hot atoms in an electric discharge emit light.

Line spectrum ( set of lines which are well

separated)
Atomic Spectra
  these are line spectra shown by atoms of elements
  the spectra of elements are dependent upon the nature
of the radiations emitted.

Important Notes:
1.) Each line in the spectrum is having a characteristic
frequency therefore it will have a definite energy.
e.g. Hydrogen Spectrum
= consists of a number of discrete lines in the visible and
ultraviolet region
2.) The change in the transition state corresponds to the
amount of energy absorbed
Atomic Spectra
H –atom absorbs only specific λ
1885  J.J. Balmer (visible light)
1886  Rydberg (u.v light)
1908  Ritz ( Infrared)
Balmer showed that for the visible lines of
hydrogen, a plot of v (frequency) vs 1/n2 gave a
straight line.

Rydberg = who put forward that the wavenumber

(cm-) of any line of the hydrogen spectrum can
be represented as a difference of two terms, one
of which is constant and the other varies
throughout the series.
Spectral Series and Rydberg integers
for the Rydberg’s Equation
Series n1 n2 Spectral Region
Lyman 1 2,3,4 ultraviolet
Balmer 2 3,4,5 Visible
Paschen 3 4,5,6 Infrared
Brackett 4 5,6,7 Infrared
Pfund 5 6,7,8 Infrared
Sample Problem
Calculate the wavelength of the second line
in the Paschen series, and show that this
line lies in the near infrared, that is, in the
infrared region near the visible

Ans:λ = 1.282 x 10-4 cm =1282 nm

1859 -1901 Black Body Radiation
 Radiation given off by materials when they are
heated ( one that absorbs and emit all frequencies and
serves as an idealization for any radiating material.)

 e.g. when an object is heated hot enough, it begins to give

off light. At first it glows a dull red. As it gets hotter, the
red color gets brighter. At high enough temperature it will
eventually glow blue.

 We see that there is a continual shift of the color of a

heated sample as temperature increases ( the
radiation goes from a lower frequency to a higher
frequency.)
 Used regularly in astronomy to estimate
the surface temperature of stars.

 e.g. solar spectrum can be approximated

as black body at around 6000K
(this temperature will give the greatest
intensity of radiation)
 If we estimate λmax to be 500 nm

 T = 2.90 x 10-3m.K / 500 x 10-9m

= 5800 K
1859: Kirchoff
 Same behavior of radiation emitted/absorbed for different
materials
 this implies something fundamental about radiation

1879: Stefan – Boltzmann Law

ε = aT4
the total energy density is proportional to the fourth power
of the temperature. (based from the area of the graph –
the area increases with the fourth power of the
temperature).
Justification: The electromagnetic field inside
the container has a definite total energy ,
which increases as the temperature.

(ε)  The total energy density is the total

energy divided by the volume of the interior
of the container.
Alternative form of the Law
 Excitance (M) = the power emitted per unit area
( brightness of the emission)

 M = σ T4 where σ = 5.67 x 10-8w/m2K

σ = Stefan Boltzmann constant

1894 : Wein Displacement Law

 Tλmax = 1/5 C2 where C2 = 1.44 cm K (second
radiation constant)
1900: Rayleigh – Jeans Law
 Studied black –body radiation from
classical viewpoint
ρ(v) dv = (8πkBT/c3) v2dv
 where :
ρV dV = radiant energy density between the
frequencies v and v + dv ( J/m3)
Limitations
 Rayleigh –Jeans formula is quite successful at
long λ and low v, but it fails badly at high v and
short λ. This failure is called “ UV breakdown/
catastrophe” (leads to infinite energy).

 The frequency increases as the radiation enters

the ultraviolet region, the divergence in the
radiant energy density as v2 (frequency) was
termed the “ultraviolet catastrophe”.
1901: Max Planck
(Quantum Theory of Radiation)
 Classical physics assumed that the light emitted from the black
body was caused by oscillations of the electrons (e-) in the
object just like oscillations of electrons in an antenna emit
radiowaves.

Physicist had always assumed that the energy of matter was

continuous which meant that the transfer of any quantity of
energy was possible.

 The first person to successfully explain black body radiation from

the viewpoint of statistical thermodynamics.

 Planck hypothesized that the energies of the oscillators were

discrete and had to be proportional to an integer multiple of the
frequency.
E = nhv where: n = 1,2,3
h = Planck’s constant
Planck’s Distribution Law
 The energy is quantized and can only be transferred in
discrete units of size hv. Each of these small “packets of
energy” is called a quantum.

dε= ρdλ
Where: ρ( λ,t) = (8πhc/λ5) (dλ/ ehc/λkT - 1)

ρ( v,t) = (8πhv3 /c3) (dv / ehv/kT - 1)

Important Notes:
1.) Planck formula reduces to the Rayleigh –Jeans Law for
long λ radiation.

2.) Planck distribution also accounts for the Stefan –

Boltzmann and Wien Law
Problem
1.)Equation ρ( v,t) = (8πhv3 /c3) (dv / ehv/kT - 1)
expresses Planck’s radiation law in terms of frequency.
Express Planck’s radiation law in terms of λ.

2.) Account that Plancks formulaρ= (8πhv3 /c3)(dv/ehv/kT - 1)

reduces to the Rayleigh – Jeans law for long wavelength of
radiation.

For short λ: ρ 0 as λ 0 and v  ∞

For long λ: ρ = (8πkBT/c3) v2dv
Stefan – Boltzmann Law
• By integrating the total energy density
over all wavelengths from λ =0 to λ = ∞
 Ev = ∫(0 to∞)ρ( v,t)

and ∫(0 to∞)(x3/ex -1) dx = π4/15

Wein’s Law
ρ( λ,t) = (8πhc/λ5) (dλ/ ehc/λkT - 1)

•dρ(λ,t) / dλ = 0 (the condition for the

maximum in the distribution at low T).
1907: Einstein
  Heat Capacity of Solids

According to Classical Mechanics

 The mean vibrational energy of each atom of a
solid is 3 KT
 For solid composed of N atoms, the total
vibrational energy : Ev = 3NkT
 The contribution of the vibrational energy to the
molar internal energy
UM = 3NkT = 3 RT
 The molar heat capacity at constant
volume is

 Cvm = (∂Um/ ∂T)V = 3R (Law of Dulong

and Petit

 Limitations of Dulong and Petit’s law

 deviations were observed when applied to

measure heat capacities at low temp.
Einstein Formula
  accounts for the decrease of heat
capacity at low temperature.
 Assumption: Each atom oscillates about
its equilibrium position with a single
frequency (v).

The molar vibrational energy of the metal

Um = (3Nhv)/ (ehv/kT – 1)
= (3Nhv) ( e-hv/kT / 1- e-hv/kt)
The Molar Vibrational energy of the
metal
 Differentiating Um with respect to T

 Cvm = 3Rf2 where f = hv/kT (ehv/2kT/ ehv/kT -1)

 At high T, Cvm = 3R

 At low T, Cvm = 0
1913: Bohr’s Model of Atom
 Postulates of Bohr’s about the moving electrons.

1.) Electrons are moving in certain definite paths

called “orbits” which have specific energies. The
angular momentum of the electron is an integral
multiple of h/2π
mvr = nh / 2 π where n is any integer
2.) Each stationary state corresponds to a definite
quantity of energy associated with it. These may
be called energy levels. These energy levels are
characterized by an integer n.
Bohr’s Model of Atom
3.) The energy level nearer the nucleus has lower
energy while that farthest from it has the
maximum energy. Electron in the level with
lowest energy is said to be in the ground state
(most stable state of the atom)
4.) If energy is made available to the electron, it
will absorb energies in packets or quanta, so that
it could move to a higher energy level.
Bohr’s Quantum Theory of H - atom
 Bohr obtained an expression for the
energy of an electron in H –atom as
follows:

Let: r = radius of the orbit in which an

electron is revolving
Assumptions
1.) Force of attraction between the electron and the nucleus
Fattraction = k Ze2/ r2 where k = 1/ 4πεo
k = 9 x 109Nm2/c2 εo = 8.854 x 10-12 F/m

2.) Centrifugal force experienced by the electron ( under the

influence of which the electron tends to fly away from the
nucleus)
Fcentrifugal force = mv2/r
3.) The electron does not fall into the nucleus
Fattraction = F centrifugal
4.) Incorporating Bohr’s quantum condition
mvr = nh/2 π
5.) When the electron is excited from n1 to n2 having E1 and E2.
E1 = -2.18 x10-18/n12 and E2 = -2.18 x 10-18/n22
 Sample Problem
Find the radius of the Bohr orbit for the most
stable state (minimum energy) of a
hydrogenic atom.
Structure of Atom (Modern Picture)
Defects of the Bohr model of atom
 It could not explain the atomic spectra of
elements other than hydrogen
Limitations :
1.) It could not account for the brightness of
spectral lines (e.g. the noble gases )
2.) No justification was given for the basis of
quantization of momentum of the electron.
 e.g. why the momentum of the electron
should have only those values which are
integral multiple of h/2π and why not
h/3π.

3.) could not explain the reason why atoms

should combine to form chemical bonds.
Relation Between Momentum and
Wavelength
 Light

Classical model : as wave

New model: as particle = made – up of

quanta/pockets (bunch of photon)
Wave – Particle duality can be
explained through
1.) Photoelectric effect
 The electromagnetic radiation displays the
characteristic of particles
 (classical physics – wave like)

2.) Experiments on Electron diffraction

 The electrons (classical physics –
particles) also display the characteristics
of waves
Particle Character of Electromagnetic
Radiation
 Observations
1.) The discrete spectra for atoms and
molecules can be pictured as the atom or
molecules generating a photon of energy
hv where it discards an energy of
magnitude ΔE
2.) The energies of electrons produced by
the photoelectric effect
3.) The Compton effect
1905: Einstein - Photoelectric
Effect
 This effect is due to the ejection of electrons from metals when
they are exposed to UV light.
 Essential Features of the Photoelectric effect
i.) No electrons are ejected, regardless of the intensity of the
radiation, unless its frequency exceeds a threshold value,
which is a characteristic of a metal
ii.) The kinetic energy of the ejected electrons varies linearly with the
frequency of the incident radiation
iii.) Even at low light intensities, electrons are ejected immediately if
the frequency is above threshold.

Albert Einstein proposed that electromagnetic radiation is quantized

(same with Planck) and suggested that electromagnetic
radiation can be viewed as a stream of “particles” called
photons. Einstein arrived at this conclusion through his analysis
of the Photoelectric effect ( for which he latter was awarded the
Nobel Prize).
Conservation of energy for
Photoelectric Effect
 K.E.= ½ mv2 = hv – Φ
where Φ = work function (characteristic
of a metal)
= energy required to remove
an electron
if hv < Φ = photoejection cannot occur
because the photon brings
insufficient energy.
 The min. frequency that will eject an electron is just the
frequency required to overcome the work function of the
metal.
Φ = hvo where vo = threshold frequency
Sample Problem
When Lithium is irradiated with light, the
kinetic energy of the ejected electron is
2.935 x 10-19J for λ = 300.0 nm. Calculate
the threshold frequency and the work
function of lithium from these data.

Ans. Vo = 5.564 x 1014 Hz

φ = 3.687 x10 -19
J = 2.301 eV
Compton Effect
 Thephotons were observed to be
scattered at all angles by the electrons of
the scattering material.

 Arthur Compton = investigated the

scattering of monochromatic x -rays by a
target such as a piece of graphite. The
scattered beam consisted of a radiation of
2 different wavelength's.
The Wave Character of electron
1.) Davisson and Germers
 Observed the diffraction of electrons by a crystal

2.) J.J Thomson

 Showed that a beam of electron was diffracted
when passed through a thin gold foil

3.) Louis de Broglie

 Suggested that any particles, not only photon
travelling with a momentum (p) should have a λ.
Quantization of Momentum
 Assumptions:

i.) the electron wave is moving in a circle

ii.) the motion of the electron should be in phase ( so that the
electron will continuously move in a circular orbit)
 in phase = constructive interference
 Out of phase = destructive interference
 Superposition of waves

Standing wave = the distance

between two points in a given wave are
invariable with time.
(only integral numbers of λ’s will form a
standing waves )
Quantization of Momentum
 Circumference of circular orbit = integral multiple of its λ.
2πr = nλ
 From de Broglie relationship
λ = h /mv

Comparing the two equations

mvr = nh / 2 π  Bohr Postulate
mvr = angular momentum of the electron
Dual Nature of Matter
1924:Louis de Broglie

 Concluded that energy is associated with

both light (wave) and matter (particle)
 Electrons have both particle and wave
properties ( every particle can be
considered to have an associated λ and
wave properties)
 λ = h/mc = h/mv  de Broglie equation
2π r = n λ  wave like properties
P = mv  particulate properties
P = h/λ  complementary properties

Sample Problem
What is the λ of a 2000 kg vehicle moving at
100 km/h?

Ans. 1.19 x 10-38m

Sample Problem
 Estimate the wavelength of electrons that have
been accelerated from rest through a potential
difference of 1.00 kV
Hint:
EK = ½mev2 = p2/2me
where: p = mev
The energy acquired by electron that falls
through a potential difference is given by:
EK = e x ΔΦ
p = (2mee ΔΦ)1/2 and λ = h / p
Ans. 3.88 x 10-11m
Implications of de Broglie Equation
In order to obtain a full mechanical
description of a free particle (no forces
acting on it) there must be a wavelength
and hence some simple oscillating function
associated with the particle’s description.
 This function can be a sine, cosine, or
equivalently, a complex exponential
function
Periodic Property of a Wave
 In 1926 Schrödinger formulated his
famous equation by applying the de
Broglie relationship to the classical wave
equation (written below in one
dimension):
Heisenberg and Schrödinger
( Quantum Mechanics)
Schrödinger ( partial differential equation)
and Heisenberg (matrices)
 to describe wave behavior

Fundamental principle of Nature : Heisenberg

Uncertainty principle

 States that it is not possible to specify both the

position and the momentum of a particle
simultaneously with infinite precision.
Δp . Δx ≈ ђ/2 or h/4π

 Likewisefor simultaneous measurements

of E and time

ΔE . Δt ≥ ђ/2
Sample Problem
Calculate the uncertainty in the position of a
baseball(5.0 oz) thrown at 90mph if we
measure its momentum to a millionth of
1.0 %.

Ans. p = 5.6 kgm/s;

1mile = 1610 m; 1lb = 16oz
Δx = 1.2 x 10-26 m
Quantum Mechanics
 The basic concept is “ energy is quantized”
e.g. spectrum of a solution
 Basically statistical in nature (probabilistic
approach) = knowing the state, we cannot
predict the result of a position measurement with
certainty, we can only predict the probabilities of
various possible results
 Associated with each physical observable
( position, momentum and energy) is a
mathematical operator. From these operator
we can predict the behavior of a physical system
Quantum Mechanics provide:
1.) the possibility of calculating energy
levels and other properties of atoms and
molecules
2.) the explanation of the periodic table
3.) the basis for understanding spectroscopy
4.) the understanding of the nature of the
chemical bond
Application of Quantum Mechanics
1.) Calculations show why properties such
as IP, EA and atom size vary in
complicated way
2.) Energy levels, bond lengths and bond
angles may be calculated quite accurately
for many small molecules
3.) Spectroscopy is useful in identifying
molecules identity and determining their
concentration
Application of Quantum Mechanics
A.) Microwave and Far IR
 Provides information on internuclear
distances and bond angles
B.) IR and Raman Spectroscopy
 Provides information about vibrational
frequencies
C.) Visible and Ultraviolet
 Provides information on dissociation
energies and electronic excited states
Failure of Classical Mechanics
 Classical mechanics cannot be applied at
microscopic levels because it is incapable
of treating such factors as
i.) electromagnetic radiation acting as
photons
ii.)photons having momentum
iii.)matter particles showing dual behavior