Physical Chemistry II

Quantum Chemistry
Chapter 12: From Classical to
Quantum Mechanics

Dr. Tarek A. Kandiel, Chemistry Department,

Office: 59-1053 (location) & 860-3762 (off. Tel)
Office hours: 10:00-11:00am (U.T.R )
Mobil: +966-54 105 2673
Tarek.kandiel@kfupm.edu.sa

Chapter 12 1
Content of Chapter 12
12.1 Why Study Quantum Mechanics?
12.2 Quantum Mechanics Arose out of the Interplay of Experiments and Theory
12.4 The Photoelectric Effect
12.5 Particles Exhibit Wave-Like Behavior
12.7 Atomic Spectra and the Bohr Model for the Hydrogen Atom

Chapter 12 2
12.1. Why Study Quantum Mechanics?
• Classical physics was unable to explain many puzzling phenomena, for
example:

➢ Why electron did not follow a spiral trajectory to end in the nucleus?

➢ Why graphite conducts electricity and diamond does not?.

➢ Why the light emitted by a hydrogen discharge lamp

appears at only a small number of wavelengths?.

• The deficiencies in classical physics promote scientists over 20 years to find

models that can describe matter at nanometer that is called ”Quantum
Mechanics”

• The central feature that distinguishes quantum and classical mechanics is

wave-particle duality.

• At the atomic level, electrons, protons, and light all behave as wave/particles
as opposed to waves or particles.
Chapter 12 3
12.2. Quantum Mechanics Arose out of the Interplay of
Experiments and Theory
• The field of quantum mechanics arose in the early 1900s as scientists
became able to investigate natural phenomena at the newly accessible
atomic level.

• At this level, they found that the predictions of classical physics were
inconsistent with experimental outcomes.

Two key properties to distinguish classical and quantum physics:

(1) The first key property is quantization: energy at the atomic level is not a
continuous variable, but it comes in discrete packets called quanta.

(2) The second key property is wave-particle duality: At the atomic level, light
waves have particle-like properties, and atoms as well as subatomic
particles such as electrons have wave-like properties.

Neither quantization nor wave-particle duality were known concepts until the
experiments described in the next sections were conducted.
Chapter 12 4
12.4. The Photoelectric Effect
• The process of electron ejection by light is called the photoelectric effect.
Classical theory predictions
(1) Light is incident as a plane wave, therefore, the light is
absorbed by many electrons in the solid.

(2) Electrons are emitted to the collector for all light

frequencies (v), provided that the light is sufficiently
intense.

(3) The kinetic energy per electron increases with the light
intensity.

Experimental observations:
(1) Number of emitted electrons is proportional to light
intensity but their kinetics is independent of the intensity.
(2) No electrons are emitted unless the “n” is above a threshold
frequency “no” even for so high light intensity.

(3) Kinetic energy for emitted electrons depends on the

frequency greater than “no” even low intensity can eject “e”.
Chapter 12 5
• Albert Einstein (1905), hypothesized that the energy of light is proportional
to its frequency

• and the energy of ejected electron, Ee, is related to the light energy by
(energy conservation):

• Where f is the work function or amount of

energy required for ionization of an atom.

• Plot of E vs, n predicted that b = h, Planck

Constant, thus

• This equation is one of the most widely used

equations in quantum mechanics and earned
Albert Einstein a Nobel Prize in physics.
Chapter 12 6
Chapter 12 7
• It was observed from photoelectric effect experiment that at a very low light
intensities, photoelectrons are emitted from the solid.

“More precisely, photoelectrons are detected even at intensities so low

that all the energy incident on the solid surface is only slightly more than
the threshold energy required to yield a single photoelectron”

• This observation indicated that “ light that liberates the photoelectron is not
uniformly distributed over the surface.

• But “ The incident light energy can be concentrated in a single electron

excitation. This led to the coining of the term photon to describe a spatially
localized packet of light”.

• Because this spatial localization is characteristic of particles, the conclusion

that light can also exhibit particle-like behavior.

Chapter 12 8
12.5. Particles Exhibit Wave-Like Behavior
• Louis de Broglie suggested that a relationship that had been derived to
relate momentum and wavelength for light should also apply to particles.

Where h is Planck constant

p is the particle momentum given by p = mv
,in which the momentum is expressed in terms of the particle mass
and velocity.

• This proposed relation was confirmed in 1927 by Davisson and Germer,

who carried out a diffraction experiment.

• Diffraction is the change in the directions and intensities of waves after

passing by or through an aperture or grating whose characteristic size is
approximately the same as the wavelength of the waves.

Chapter 12 9
 Classical view of electron (as only particle) Electrons as particle-wave duality
(observation)

• Based on Louis de Broglie relation, it is difficult to obtain wavelengths

much longer than 1 nm with particles as the electron.

• Therefore, diffraction requires a grating with atomic dimensions, and an ideal

candidate is a crystalline solid.

• Davisson and Germer observed diffraction of electrons from crystalline

NiO in their classic experiment to verify the de Broglie relation.
Chapter 12 10
• The below figure shows a scan through a diffraction pattern obtained by
diffracting a beam of He atoms from a crystal surface of nickel.

• Diffraction scan obtained by rotating a

mass spectrometer around a nickel
single crystal surface on which a
collimated He beam was incident.

• Davisson-Germer experiment was critical in the development of quantum mechanics in that it

showed that particles exhibit wave behavior.
Chapter 12 11
p =mv

Chapter 12 12
12.7. Atomic Spectra and the Bohr Model of the Hydrogen
Atom
• The most direct evidence of energy quantization
comes from the analysis of the light emitted from
highly excited atoms in a plasma.

• Based on scattering of alpha particles, Ernest

Rutherford’s atom contains positive charge in
the nucleus, and negative charge of electrons.

• In a classical picture, the electron would

continually radiate away its kinetic energy and
eventually fall into the nucleus as depicted in the
figure.

• Even before Rutherford’s experiments, it was

known that if an electrical arc is placed across a
vacuum tube with a small partial pressure of
hydrogen, light is emitted.
Chapter 12 13
• Our present picture of this phenomenon is that the atom takes up energy
from the electromagnetic field and makes a transition to an excited state.
The excited state has a limited lifetime, and when the transition to a state of
lower energy occurs, light is emitted.

• An apparatus used to obtain atomic spectra and a typical spectrum are

shown schematically in the figure.

➢ The experimental observation

made is that over a wide range of
wavelengths, light emitted from
atoms is only observed at certain
discrete wavelengths; that is
quantized.

• This result was not

understandable on the basis of
classical theory because in
classical physics, energy is a
continuous variable.

Chapter 12 14
• It was observed that the inverse of the wavelength of all lines in an atomic
hydrogen spectrum is given by an empirical relation:

Where RH is called the Rydberg constant (109,677.581 cm-1) and n is integer number

What is this relation? Why n can only take integer values?

Bohr model:

• Bohr assumed a simple model of the hydrogen atom in which an electron revolved around
the nucleus in a circular orbit.

• The orbiting electron experiences two forces: a Coulombic attraction to the nucleus,
and a centrifugal force that is opposite in direction. In a stable orbit, these two forces
are equal.

e is the charge on the electron, me and v are its mass and speed, and r is the orbit radius.
Chapter 12 15
• Bohr next introduced wave-particle duality by asserting that the electron had the de Broglie
wavelength.

• He made a new assumption that the length of an orbit had to be an integral number of
wavelengths.

p =mev
• Which leads to the condition:

• Bohr reasoned that unless the orbit length is an

integral number of wavelengths, the wave will
destructively interfere with itself, and the
amplitude will decrease to zero.

• Solving in v and substitution in:

gives

• This eq. shows that the electron can only have

certain discrete values for the orbit radii, each
corresponding to a different value of n. Chapter 12 16
Chapter 12 17
Bohr model of the Hydrogen atom
• The total energy of the electron in the hydrogen atom is the sum of its kinetic and potential
energies.

Coulombic attraction to the nucleus, and

a centrifugal force are equal
(solving in v and substitution)

substitution
• All energy values have
negative values.
• Because arbitrarily the
zero energy
correspond to n →∞
Chapter 12 18
• Because the energy of the electron can have only certain discrete values, the light emitted
when an electron makes a transition from a higher to a lower energy level has a discrete set of
frequencies:

• This finding provides rational

explanation for the empirical relation of:

• Bohr model explains nicely for

absorption and emission spectra of
Hydrogen atom.
• But not other atoms with more than 1
electrons.
• Need a theory upgrade!
• Need a more general theory that can
explain/describe quantum phenomena.
Chapter 12 19