THREE FAILURES OF CLASSICAL

PHYSICS
1. Blackbody Radiation
Any object with a temperature above absolute zero emits light at all wavelengths. If
the object is perfectly black (so it doesn't reflect any light), then the light that comes
from it is called blackbody radiation.

The energy of blackbody radiation is not shared evenly by all wavelengths of light.
The spectrum of blackbody radiation (below) shows that some wavelengths get more
energy than others. Three spectra are shown, for three different temperatures. (One of
the curves is for the surface temperature of the Sun, 5770 K.)

Here are some experimental facts about blackbody radiation:

a. The blackbody spectrum depends only on the temperature of the object, and not on
what it is made of. An iron horseshoe, a ceramic vase, and a piece of charcoal --- all
emit the same blackbody spectrum if their temperatures are the same.

b. As the temperature of an object increases, it emits more blackbody energy at all

wavelengths.

c. As the temperature of an object increases, the peak wavelength of the blackbody

spectrum becomes shorter (bluer). For example, blue stars are hotter than red stars.

d. The blackbody spectrum always becomes small at the left-hand side (the short
wavelength, high frequency side).

The explanation of classical physics: Light is an electromagnetic wave that is

produced when an electric charge vibrates. (Strictly speaking, "vibrates" means any
change in how the charge moves --- speeding up, slowing down, or changing
direction.) Now recall that heat is just the kinetic energy of random motion. In a hot
object, electrons vibrate in random directions and produce light as a result. A hotter
object means more energetic vibrations and so more light is emitted by a hotter object
--- it glows brighter. So far, so good. But classical physics could not explain the shape
of the blackbody spectrum.

The electrons in a hot object can vibrate with a range of frequencies, ranging from
very few vibrations per second to a huge number of vibrations per second. In fact,
there is no limit to how great the frequency can be. Classical physics said that each
frequency of vibration should have the same energy. Since there is no limit to how
great the frequency can be, there is no limit to the energy of the vibrating electrons at
high frequencies. This means that, according to classical physics, there should be no
limit to the energy of the light produced by the electrons vibrating at high
frequencies. WRONG!!Experimentally, the blackbody spectrum always becomes
small at the left-hand side (short wavelength, high frequency).

At about 1900, Max Planck came up with the solution. He proposed that the classical
idea that each frequency of vibration should have the same energy must be wrong.
Instead, he said that energy is not shared equally by electrons that vibrate with
different frequencies. Planck said that energy comes in clumps. He called a clump of
energy a quantum. The size of a clump of energy --- a quantum --- depends on the
frequency of vibration. Here is Planck's rule for the a quantum of energy for a
vibrating electron:

energy of a quantum = (a calibration constant) x (frequency of vibration)

or

E = hf

where h, the calibration constant, is today called Planck's constant. Its value is about 6
x 10-34, very tiny!

So how does this explain the spectrum of blackbody radiation? Planck said that an
electron vibrating with a frequency f could only have an energy of 1 hf, 2 hf, 3 hf, 4 hf,
... ; that is,

energy of vibrating electron = (any integer) x hf

But the electron has to have at least one quantum of energy if it is going to vibrate. If
it doesn't have at least an energy of 1hf, it will not vibrate at all and can't produce any
light. "A ha!" said Planck: at high frequencies the amount of energy in a quantum, hf,
is so large that the high-frequency vibrations can never get going! This is why the
blackbody spectrum always becomes small at the left-hand (high frequency) side.

2. The Photoelectric Effect

When light shines on the surface of a metallic substance, electrons in the metal absorb
the energy of the light and they can escape from the metal's surface. This is called
the photoelectric effect, and it is used to produce the electric current that runs many
solar-powered devices. Using the idea that light is a wave with the energy distributed
evenly throughout the wave, classical physicists expected that when using very dim
light, it would take some time for enough light energy to build up to eject an electron
from a metallic surface. WRONG!! Experiments show that if light of a certain
frequency can eject electrons from a metal, it makes no difference how dim the light
is. There is never a time delay.

In 1905, Albert Einstein came up with the solution. If Max Planck's idea that energy
comes in clumps (quanta) is correct, then light must consist of a stream of clumps of
energy. Each clump of light energy is called a photon, said Einstein, and each photon
has an energy equal to hf (Planck's constant times the frequency of the light).
Therefore the energy of light is not evenly distributed along the wave, but is
concentrated in the photons. A dimmer light means fewer photons, but simply turning
down the light (without changing its frequency) does not alter the energy of an
individual photon. So for a specific frequency light, if a single photon has enough
energy to eject an electron from a metallic surface, then electrons will always be
ejected immediately after the light is turned on and the photons hit the metal.
3. The Hydrogen Atom
When a small tube of hydrogen gas is heated, it begins to glow and emit light. Unlike
the blackbody radiation that comes from a hot dense solid or gas, this light consists of
just a few colors (wavelengths): a red wavelength, a turquoise, and several violets.
Classical physicists at the beginning of the century thought they should certainly be
able to understand hydrogen, since it is the simplest atom. Hydrogen consists of a
positively charged proton at the center, with a negatively charged electron orbiting
around it. The electrical attraction between the positive proton and the negative
electron keeps the electron in orbit, just like the gravitational attraction between the
Sun and the Earth holds the Earth in orbit. There was just one problem. Classical
physics said that because the orbiting electron is constantly changing direction, it
should emit electromagnetic radiation --- light. As a result, the electron should be
continually losing energy. In fact, physicists calculated that the electron should lose
all of its energy and spiral down into the proton in only about 0.000000000001
second! In other words, atoms should not exist longer than a mere 10-
12
seconds. WRONG!!

Niels Bohr provided an explanation in 1913. In the Bohr model of the hydrogen atom,
the electron can't orbit the proton in any size orbit it pleases. There are only certain
allowed orbits, and each allowed orbit has a certain radius and a certain energy. Bohr
invented a rule that allowed him to calculate the size and energy of each orbit. If you
are curious, Bohr's rule said that

2π x (electron mass) x (electron orbital speed) x (orbit radius) = (any integer) x h

which is not too obvious, to say the least! (The integer would be 1 for the smallest
orbit, 2 for the next orbit out, and so on.) Bohr also made up a new rule to explain the
stability of the hydrogen atom --- why it could last longer than 0.000000000001
second. He said that when an electron is in an allowed orbit, the electron will not
produce electromagnetic radiation. Bohr did not explain why, he just proposed a new
law of nature. And nature agreed with Niels Bohr. His new model of hydrogen gave
wavelengths for hydrogen gas that precisely agreed with what was measured.

Question: If the electrons do not produce light when they are in their allowed stable
orbits, where is the source of the light that comes from hydrogen? Answer: According
to Bohr, electrons have more energy when they are in larger orbits. If an electron falls
from a larger orbit down to a smaller orbit, it loses energy. According to the law of
conservation of energy, the energy lost by the electron must go somewhere. Bohr
explained that a photon carries away the lost energy from the hydrogen atom; that is,

photon energy = (electron energy in larger orbit) - (electron energy in smaller orbit)

It works the other way, too. If a photon strikes an atom, the atom can absorb the
photon and its energy if (and only if) the photon's energy is exactly equal to
the difference between two orbital energies. In this case, an electron uses the photon's
energy to jump from the smaller orbit up to the larger orbit. This is called a quantum
jump.

The electron falls down to a lower orbit and the A photon is absorbed by the atom, which gains
atom loses energy. A photon carries away the the photon’s energy. The electron uses this
energy lost by the atom. energy to jump up to a higher orbit.
 WAVES OR PARTICLES? BOTH!
When light passes through a double-slit, an interference pattern consisting of bright
bands and dark bands is seen on a screen. This is produced when the wave from one
slit combines with the wave from the other slit. If two wave crests meet at the screen,
the waves add and you get a bright band. If a wave crest from one slit meets a wave
trough from the other slit, the waves cancel and you get a dark band. This proves that
light is a wave.

On the other hand, the photoelectric effect proves that light consists of massless
particles called photons.

So which is it? Is light a wave or a stream of particles? The answer is "Yes!"

Light acts like a wave if you want to know how it propagates, how it travels from one
place to another. To describe how light travels from the double slits to the screen, you
have to use the wave characteristics of light.

Light acts like particles (photons) if you want to know how light interacts with matter.
To describer how light interacts with the electrons in a metal and how it ejects them
from the metal's surface, you have to use the particle characteristics of light.

We say that light exhibits a wave-particle duality. It can behave like either waves or
particles (but not both at the same time), depending on the situation.

Thinking about the photoelectric effect again, how can a photon (which has no mass)
knock an electron about? Einstein used his theory of relativity to show that even
massless photons have momentum. Newton defined momentum = (mass) x (velocity)
for a particle with mass, but Einstein was able to show that the momentum of a
massless photon depends on its wavelength:

The smaller the wavelength, the greater the momentum of the photon.

In 1923, Prince Louis de Broglie of France had an idea. Maybe the wave-particle
duality applies to everything in nature. He proposed that everything propagates like a
wave, and that everything interacts like a particle. Say what?? What do you mean by
the wavelength of an electron, or the wavelength of a baseball? De Broglie rewrote
Einstein's formula for the momentum of a photon and applied it to a particle with
mass:
Planck's constant, h, is so tiny that we don't notice the wavelength of a thrown
baseball, which is only about 10-35 meters! But an electron's mass is also tiny, so it has
a wavelength about 10,000 times shorter than the wavelength of visible light. This is
useful, because microscopes that use electron waves instead of light waves can see
several thousand times more detail!

The proof that electrons propagate like a wave came when electrons were passed
through a double slit and counted as they hit a screen. If the electrons traveled like a
stream of particles, they would have simply piled up at two locations behind the two
slits. But they didn't. They showed a double-slit interference pattern, bright bands and
dark bands just like the ones produced by light waves. Without a doubt, electrons
exhibit the wave-particle duality of nature. In fact, every massive object exhibits the
wave-particle duality of nature. It just isn't noticeable on the large scale of our
everyday world.

SUMMARY
If you look at most of the "equations" above, you will find Planck's constant, h. This
is the trademark of "modern physics." The failure of classical physics to explain
blackbody radiation, the photoelectric effect, and the hydrogen atom ultimately
demolished the foundations of classical physics.

Max Planck, Albert Einstein, Niels Bohr, and Louis de Broglie made inspired guesses
about how nature works. Other people of their time made different guesses. Nature
agreed with Planck, Einstein, Bohr, and de Broglie, but not with the others whose
names are now forgotten. Like Arcadia's Thomasina, these were intuitive geniuses
who went beyond mere mathematics to make creative conjectures about how the
world operates. Those who came later calculated the consequences of the new
physics, but this was just mathematics (sometimes brilliant mathematics, but
mathematics nonetheless). It is those rare intuitive geniuses who courageously discard
the old rules and invent new ones who are in the first rank of physicists.

Finally, It is important to remember that Planck's constant is very tiny, only about 6 x
10-34. Roughly speaking, this means that in our everyday world, quantum effects like
the wave-particle duality make a difference only in the 34th decimal place when
predicting the behavior of a moving baseball. Large objects obey Newton's laws. But
the behavior of large object reflect the average behavior of their component atoms, so
it is fair to say that Newton's laws work only "on average." The behavior of small
systems is radically different than what classical physics predicts. Ultimately, the
whole idea of prediction --- that the same conditions should always produce the same
results --- was overthrown. This is explained in Chapter 6 of Richard Feynman's The
Character of Physical Law.

Return to Honors 1500 home page

Last modified: Sunday, May 08, 2005 06:03 PM

http://physics.weber.edu/carroll/honors/failures.htm

Classical and Quantum Mechanics - in a

Nutshell
Classical Mechanics

Building on the work of Galileo and others, Newton unveiled his laws of motion in
1686. According to Newton:

I. A body remains at rest or in uniform motion (constant velocity - both speed and
direction) unless acted on by a net external force.

II. In response to a net external force, , a body of mass m accelerates with

acceleration .

III. If body i pushes on body j with a force , then body j pushes on body i with a

force .

For energy-conserving forces, the net force on particle i is the negative gradient
(slope in three dimensions) of the potential energy with respect to particle i's

position: , where represents the potential energy of the system

as a function of the positions of all N particles, . In three dimensions, is the

vector of length 3 specifying the position of the atom, and is the vector of
length specifying all coordinates. In the context of simulation, the forces are
calculated for energy minimizations and molecular dynamics simulations but are not
needed in Monte Carlo simulations.

Classical mechanics is completely deterministic: Given the exact positions and

velocities of all particles at a given time, along with the function , one can
calculate the future (and past) positions and velocities of all particles at any other
time. The evolution of the system's positions and momenta through time is often
referred to as a trajectory.

Quantum Mechanics

A number of experimental observations in the late 1800's and early 1900's forced
physicists to look beyond Newton's laws of motion for a more general theory. See, for
example, the discussion of the heat capacity of solids. It had become increasingly
clear that electromagnetic radiation had particle-like properties in addition to its wave-
like properties such as diffraction and interference. Planck showed in 1900 that
electromagnetic radiation was emitted and absorbed from a black body in discrete
quanta, each having energy proportional to the frequency of radiaion. In 1904,
Einstein invoked these quanta to explain the photo-electric effect. So under certain
circumstances, one must interpret electromagnetic waves as being made up of
particles. In 1924 de Broglie asserted that matter also had this dual nature: Particles
can be wavey.

To make a long and amazing story [1] short, this led to the formulation of
Shrödinger's wave equation for matter:

Don't let the brevity of notation fool you; this partial differential equation is difficult
to deal with and generally impossible to solve analytically. It is tailored to a given
physical system by defining theHamiltonian operator to incorporate all the
relevant forces exerted on the particles of the system. The solution of this equation
yields the discrete (quantized) values (or eigenvalues) of energy , and for
each its corresponding wave function . In general, these wave functions

are complex-valued functions (involving ), but the quantity is

always real and thus may correspond to something physical. ( is the `complex
conjugate' of .) In fact, is a probability density. For motion in the single
dimension x, it is `a probability per unit x': is the probability that the particle
will be found at a position between x and . The wavefunctions
are normalized (scaled) by the requirement that the particle must be somewhere, i.e.,
that these probabilities must sum to one:

Quantum mechanics is thus not deterministic, but probabilistic. It forces us to abandon

the notion of precisely defined trajectories of particles through time and space.
Instead, we must talk in terms ofprobabilities for alternative system configurations.

To clarify these concepts, consider two major successes for the quantum theory,
predictions of the discrete energy levels of the harmonic oscillator and the hydrogen
atom. Pictured below are the potential energy (solid lines) and the four lowest energy
levels (dashed lines) for a one dimensional harmonic oscillator (red) and the three
dimensional hydrogen atom (blue). The harmonic oscillator depicted corresponds to a
hydrogen atom oscillating at the frequency f = 100/ps and represents one of the
highest frequency atomic motions in macromolecules. The energy levels of harmonic
oscillators are equally spaced, separated by an energy of hf, or 9.5 kcal/mol for the
oscillator shown. The energy gaps for a hydrogen atom oscillating at f = 10/ps are
0.95 kcal/mol, on the order of thermal energy, and so classical mechanics better
approximates quantum results (e.g., average energy and motional amplitude) for this
slower oscillator.

Excitation of electrons within atoms requires much more energy than excitation of
atomic vibrations. Promotion of the hydrogen atom's electron from its ground state to
its first excited state requires 235 kcal/mol. Way beyond the reach of thermal energy,
this excitation requires the absorption of ultraviolet radiation with a wavelength of
121 nm.
 Potential and four lowest E levels
for a harmonic oscillator (red) and the hydrogen atom (blue).

http://cmm.cit.nih.gov/intro_simulation/node1.html

The Problems with Classical Physics

By the late nineteenth century the laws of physics were based on Mechanics and the
law of Gravitation from Newton, Maxwell's equations describing Electricity and
Magnetism, and on Statistical Mechanics describing the state of large collection of
matter. These laws of physics described nature very well under most conditions,
however, some measurements of the late 19th and early 20th century could not be
understood. The problems with classical physics led to the development of Quantum
Mechanics and Special Relativity.

Some of the problems leading to the development of Quantum Mechanics are listed
here.

 Black Body Radiation: Classical physics predicted that hot objects would
instantly radiate away all their heat into electromagnetic waves. The
calculation, which was based on Maxwell's equations and Statistical
Mechanics, showed that the radiation rate went to infinity as the EM
wavelength went to zero, ``The Ultraviolet Catastrophe''. Plank solved the
 problem by postulating that EM energy was emitted in quanta

with .
 The Photoelectric Effect: When light was used to knock electrons out of solids,
the results were completely different than expected from Maxwell's
equations. The measurements were easy to explain (for Einstein) if light is
made up of particles with the energies Plank postulated.
 Atoms: After Rutherford found that the positive charge in atoms was
concentrated in a very tiny nucleus, classical physics predicted that the atomic
electrons orbiting the nucleus would radiate their energy away and spiral into
the nucleus. This clearly did not happen. The energy radiated by atoms also
came out in quantized amounts in contradiction to the predictions of classical
physics. The Bohr Atom postulated an angular momentum quantization rule,

for , that gave the right result for

hydrogen, but turned out to be wrong since the ground state of hydrogen has
zero angular momentum. It took a full understanding of Quantum Mechanics
to explain the atomic energy spectra.
 Compton Scattering: When light was scattered off electrons, it behaved just
like a particle but changes wave length in the scattering; more evidence for
the particle nature of light and Plank's postulate.
 Waves and Particles: In diffraction experiments,light was shown to behave like
a wave while in experiments like the Photoelectric effect, light behaved like a
particle. More difficult diffraction experiments showed that electrons (as well
as the other particles) also behaved like a wave, yet we can only detect an
integer number of electrons (or photons).

Quantum Mechanics incorporates a wave-particle duality and explains all of the

above phenomena. In doing so, Quantum Mechanics changes our understanding of
nature in fundamental ways. While the classical laws of physics are deterministic, QM
is probabilistic. We can only predict the probability that a particle will be found in
some region of space.

Electromagnetic waves like light are made up of particles we call photons. Einstein,
based on Plank's formula, hypothesized that the particles of light had energy
proportional to their frequency.
The new idea of Quantum Mechanics is that every particle's probability (as a function
of position and time) is equal to the square of a probability amplitude function and
that these probability amplitudes obey a wave equation. This is much like the case in
electromagnetism where the energy density goes like the square of the field and hence
the photon probability density goes like the square of the field, yet the field is made
up of waves. So probability amplitudes are like the fields we know from
electromagnetism in many ways.

DeBroglie assumed for photons and other particles and used Lorentz
invariance(from special relativity) to derive the wavelength for particles like
electrons.

The rest of wave mechanics was built around these ideas, giving a complete picture
that could explain the above measurements and could be tested to very high
accuracy, particularly in the hydrogen atom. We will spend several chapters
exploring these ideas.

* Example: Assume the photon is a particle with the standard deBroglie wavelength.
Use kinematics to derive the wavelength of the scattered photon as a function of angle
for Compton Scattering.*

Gasiorowicz Chapter 1

Rohlf Chapters 3,6

Griffiths does not really cover this.

Cohen-Tannoudji et al. Chapter

 Subsections

 Black Body Radiation *

 The Photoelectric Effect
 The Rutherford Atom *
 Atomic Spectra *
o The Bohr Atom *

 Derivations and Computations

o Black Body Radiation Formulas *
o The Fine Structure Constant and the Coulomb Potential

 Examples
o The Solar Temperature *
o Black Body Radiation from the Early Universe *
o Compton Scattering *
o Rutherford's Nuclear Size *

 Sample Test Problems

http://quantummechanics.ucsd.edu/ph130a/130_notes/node47.html

Classical vs. Quantum Mechanics

Table of Contents

1. Introduction
2. Blackbody radiation
3. Photoelectric effect
4. Molar heat capacity at constant volume (Cv)
5. Conclusion
6. Summary
7. References
8. Outside Links
9. Problems
Classical mechanics consists of the work done in the areas of chemistry and physics prior to the 20th century. This
includes the organization of the periodic table, thermodynamics, the wave theory of light, and Newtonian
mechanics. Quantum mechanics was born out of the inability of classical mechanics to reconcile theory with
experiment.

Introduction
Some of the areas in which discrepancies were observed between the classical model and experiment are: blackbody
radiation, the photoelectric effect, and heat capacity.

Blackbody radiation
Blackbody radiation provided a famous incongruity between theory and experiment for classical physics. Classically,
the radiant energy density dρ was described by the following equation:

dρ(ν,T)=8πκBTc3ν2dν
This led to the problem known as the "UV catastrophe." As the frequency of light ν increases the radiant energy density
approaches infinity (Figure 1). However, this trend was not observed in the experiments. In fact, the radiant energy
density was found to decrease as the frequency increased in the UV spectrum.

In 1900, Max Planck successfully explained blackbody radiation and derived the following equation to accurately
describe the experimental results:

dρ(ν,T)=8πhc3ν3dνehνκBT−1
Planck was able to derive this formula by assuming that the energies of the oscillators were quantized
(i.e. E=nhν, where h is Planck's constant h=6.626∗10−34Js. Planck's quantization of energy was a revolutionary
assumption that marked the beginning of a new field of chemistry aptly named quantum mechanics.

Figure 1: Line plot depicting the classical model of blackbody radiation overlapped with the quantum model of blackbody
radiation. The quantum model agrees with the experimental values whereas the classical model diverges at high
frequencies. This divergence is what is referred to as the UV catastrophe.

Notice that as the frequency of the radiation decreases the quantum prediction approaches the classical prediction.
Photoelectric effect

Another phenomenon in which a quantized approach was used to explain the experimental results is the photoelectric
effect. Classical physics describes light as a wave (electromagnetic radiation) with a set frequency and amplitude where
the amplitude is related to the intensity. Light was observed to cause electrons to be ejected from a metal's surface. The
classical explanation was that the metal's electrons would oscillate with the light and eventually break away from the
surface with a kinetic energy that would depend on the intensity of the incident radiation because the higher the intensity
the higher the amplitude of the oscillation. However, the kinetic energy of the ejected electrons was shown to be
independent of the intensity of the radiation. In fact, there were some frequencies that no matter how intense the
incident radiation was no electrons were ejected.

Einstein modified Planck's concept of quantized energy to describe the experimental results. Einstein proposed that
light could travel in small quantized packets of energy (photons) instead of strictly behaving as a classical
wave. Einstein showed that the kinetic energy of the ejected electrons was equal to the energy of the incident photon
(hν) minus the energy barrier to releasing an electron from that particular metal (workfunction= ϕ). This interpretation
is described by the following equation:

KE=12mv2=hν−ϕ

This model was able to fully account for the experimental results including the lack of dependence of the energy of the
ejected photons on the intensity of the incident radiation as well as the failure of some frequencies of light to eject any
photons (the incident energy of the photon was less than the workfunction).
One important result of Einstein's work with the photoelectric effect (outside of the concept of the photon) was the fact
that his experimentally determined value of h was the same value determined by Planck. This gave credence to the
idea of quantized energy and quantum chemistry as a whole, which was still viewed with suspicion by many scientists.

Molar heat capacity at constant volume ( Cv)

Classically, the molar heat capacity at constant volume is equal to 3R where R is the molar gas constant
(8.314JK−1mol−1). This model was found to hold true at high temperatures, but to break down as the temperature is
decreased. Einstein relied on a quantum interpretation to explain why the experimental results deviated from the
classical prediction at low temperatures.

Einstein proposed that the physical oscillations of the atoms in the crystal matrix are subject to quantized vibrational
states where the change of position of the atom in the lattice (Δε) is represented by the equation:

Δε=hν
 Figure 2: Line plot of the classical and quantum models for heat capacity at constant volume.

Notice that as the temperature increases, the quantum model approaches the classical model. This was an interesting
addition to quantum theory because it extended the concepts beyond light and electrons to the mechanical vibrations
of whole atoms.
 Conclusion
Classical mechanics accurately describes most systems that can be easily observed. Objects that are a "normal" size
(larger than a molecule and smaller than a planet), at a "normal" temperature (anywhere close to room temperature),
going a normal speed (0 m/s- anything significantly less than the speed of light) fit the models set forth in classical
mechanics. It is only when the system being observed begins to violate these parameters that quantum factors come
into play. An important aspect of the quantum mechanical models is the fact that as the conditions approach "normal"
the quantum mechanical model approaches the classical model.

Summary
Quantum mechanics approaches Classical mechanics when:

 ν→0: This is observed in the phenomenon of blackbody radiation (Figure 1).

 t→∞: This is observed in the phenomenon of heat capacity (Figure 2).
 h→0: This is observed when taking the limit as h→0 for the average quantum mechanical energy (hνehνkBT−1). Notice
that this limit is equal to the average classical energy ( kBT).
 n→∞: This is known as the Bohr correspondence (Figure 3).

Figure 3: Line graph of the probability of finding a particle at a given position for two wave equations evaluated at
different n's.

Notice that as n increases, the probability function approaches a straight line. Classically, the probabilty of finding a
particle is independent of position (a straight line with a constant y value). Thus, as n increases, the quantum model
approaches the classical model. This is known as the Bohr correspondence.
 References
1. McQuarrie, Donald A. Quantum Chemistry. 2nd ed. United States Of America: University Science Books, 2008.

Outside Links
 Wikipedia: Quantum Mechanics
 Wikipedia: Classical Mechanics
 Cambridge University Press: Classical Mechanics vs. Quantum Mechanics
 Classical and Quantum Mechanics in a nut shell

Problems
1. Prove that taking the limit as h→0 for the average quantum mechanical energy (hνehνkBT−1) yields the average
classical energy (kBT). (Hint: use l'Hôpital's rule)

http://chemwiki.ucdavis.edu/Physical_Chemistry/Quantum_Mechanics/01._Waves_a
nd_Particles/Classical_vs._Quantum_Mechanics

FAILURE OF CLASSICAL PHYSICS

(a) Black Body Radiation: Classical Physics failed to explain Black Body spectrum of
radiation over all frequency ranges, which came to be known as UV catastrophe. There
was an in- congruency between theory and experiment. Classically, the radiant energy
density dρ was described by the following equation:

dρ(ν,T)=8πκBTν2dν/c3

The above formulation proves that as the frequency of light ν increases the radiant energy
density approaches infinity as shown in Figure 1. However, the experimental results
contradict the theory. In fact, it was established by experiments that the radiant energy
density tends to decrease as the frequency increased in the UV spectrum.
Fig. 1: A comparison of the classical and the quantum models of blackbody radiation. The
quantum model explains experimental values at all ranges of frequencies whereas the
classical model fails at high frequencies. Classical model and quantum models agree at
low frequencies.

Max Planck (1900) successfully explained blackbody radiation and derived the
following equation to accurately describe the experimental results (refer to Figure 1):

dρ(ν,T)=8πh/c3 (ν3dν/ehν/κBT −1)

Planck was able to derive this formula by assuming that the energies of
the oscillators
were quantized (i.e. E=nhν, where h is Planck's constant = 6.626x10-
34
J-s. Planck's quantization of energy was a revolutionary assumption
that marked the beginning of a new field of Quantum Physics.

(b) Photoelectric Effect: Quantum Physics approach was used to explain

the experimental results of the photoelectric effect, which is simply
ejection of electrons from a metal surface when light beam falls on it.
Classical physics describes light as a wave with a set frequency and
amplitude where the amplitude is related to the intensity. The classical
explanation was that the metal's electrons would oscillate with the light
and eventually break away from the surface with
a kinetic energy that would depend on the intensity of the incident
radiation. However, the experimental observations show that the kinetic
energy of the ejected electrons is independent of the intensity of the
radiation. In fact, no electrons were ejected,no matter how intense the
incident radiation was, if frequency of light beam is lower than a given
threshold frequency for that metal.

Planck's concept of quantized energy was used by Einstein in a modified

form to describe the experimental results of Photoelectric effect. Einstein
proposed that light could travel in small quantized packets of energy
(photons) instead of strictly behaving as a classical wave. Einstein
showed that the kinetic energy of the ejected electrons was equal to the
energy of the incident photon minus the energy barrier (known as work
function ϕ) to releasing an electron from that particular metal. This
interpretation is described by the following equation:
 KE=1/2 mv2 =hν−ϕ

Thus Einstein model was able to fully account for the experimental
results including the lack of dependence of the energy of the ejected
photons on the intensity of the incident radiation.The failure of some
frequencies of light to eject any photons from the metal surface is based
on the fact that the incident photons have energy less than the work
function of the metal.

Photoelectric effect was used by Einstein to experimentally determine

the value of Planck constanth, whichproved to be the same as
determined by Planck. This gave credence to the idea of quantized
energy and Quantum Physics as a whole, which was still viewed with
suspicion by many scientists including Einstein.

Classical Physics versus Quantum Physics:

An Overview

Hardev Singh Virk

Visiting Professor, SGGS World University, Fatehgarh
Sahib (Punjab) – 140426, India

Abstract

Chapter 1

Origins of Quantum Physics

In this chapter we are going to review the main physical ideas and
experimental facts that defied classical physics and led to the birth of
quantum mechanics. The introduction of quan- tum mechanics was
prompted by the failure of classical physics in explaining a number of
microphysical phenomena that were observed at the end of the
nineteenth and early twentieth centuries.

1.1 Historical Note

At the end of the nineteenth century, physics consisted essentially of

classical mechanics, the theory of electromagnetism1, and
thermodynamics. Classical mechanics was used to predict the
dynamics of material bodies, and Maxwell’s electromagnetism
provided the proper frame- work to study radiation; matter and
radiation were described in terms of particles and waves, respectively.
As for the interactions between matter and radiation, they were well
explained by the Lorentz force or by thermodynamics. The
overwhelming success of classical physics— classical mechanics,
classical theory of electromagnetism, and thermodynamics—made
people believe that the ultimate description of nature had been
achieved. It seemed that all known physical phenomena could be
explained within the framework of the general theories of matter

and radiation.

At the turn of the twentieth century, however, classical physics, which

had been quite unas- sailable, was seriously challenged on two major
fronts:

7 Relativistic domain: Einstein’s 1905 theory of relativity showed that

the validity of Newtonian mechanics ceases at very high speeds (i.e.,
at speeds comparable to that of light).

7 Microscopic domain: As soon as new experimental techniques were

developed to the

point of probing atomic and subatomic structures, it turned out that

classical physics fails miserably in providing the proper explanation for
several newly discovered phenomena.
It thus became evident that the validity of classical physics ceases at
the microscopic

level and that new concepts had to be invoked to describe, for

instance, the structure of

atoms and molecules and how light interacts with them.

1Maxwell’s theory of electromagnetism had unified the, then ostensibly

different, three branches of physics: elec-

tricity, magnetism, and optics.

1
2 CHAPTER 1. ORIGINS OF QUANTUM PHYSICS

The failure of classical physics to explain several microscopic

phenomena—such as black- body radiation, the photoelectric effect,
atomic stability, and atomic spectroscopy—had cleared

the way for seeking new ideas outside its purview.

The first real breakthrough came in 1900 when Max Planck introduced
the concept of the quantum of energy. In his efforts to explain the
phenomenon of blackbody radiation, he suc- ceeded in reproducing
the experimental results only after postulating that the energy
exchange between radiation and its surroundings takes place in
discrete, or quantized, amounts. He ar- gued that the energy exchange
between an electromagnetic wave of frequency F and matter occurs
only in integer multiples of hF, which he called the energy of a
quantum, where h is a fundamental constant called Planck’s constant.
The quantization of electromagnetic radiation

turned out to be an idea with far-reaching consequences.

Planck’s idea, which gave an accurate explanation of blackbody

radiation, prompted new thinking and triggered an avalanche of new
discoveries that yielded solutions to the most out-

standing problems of the time.

In 1905 Einstein provided a powerful consolidation to Planck’s

quantum concept. In trying to understand the photoelectric effect,
Einstein recognized that Planck’s idea of the quantization of the
electromagnetic waves must be valid for light as well. So, following
Planck’s approach, he posited that light itself is made of discrete bits of
energy (or tiny particles), called photons, each of energy hF, F being
the frequency of the light. The introduction of the photon concept
enabled Einstein to give an elegantly accurate explanation to the
photoelectric problem, which

had been waiting for a solution ever since its first experimental
observation by Hertz in 1887.

Anotherseminalbreakthrough wasduetoNielsBohr. Right

afterRutherford’sexperimental discovery of the atomic nucleus in 1911,
and combining Rutherford’s atomic model, Planck’s quantum concept,
and Einstein’s photons, Bohr introduced in 1913 his model of the
hydrogen atom. In this work, he argued that atoms can be found only
in discrete states of energy and that the interaction of atoms with
radiation, i.e., the emission or absorption of radiation by atoms, takes
place only in discrete amounts of hF because it results from transitions
of the atom between its various discrete energy states. This work
provided a satisfactory explanation to

several outstanding problems such as atomic stability and atomic

spectroscopy.

Then in 1923 Compton made an important discovery that gave the

most conclusive confir- mation for the corpuscular aspect of light. By
scattering X-rays with electrons, he confirmed that the X-ray photons
behave like particles with momenta hFnc; F is the frequency of the

X-rays.

This series of breakthroughs—due to Planck, Einstein, Bohr, and

Compton—gave both the theoretical foundations as well as the
conclusive experimental confirmation for the particle aspect of waves;
that is, the concept that waves exhibit particle behavior at the
microscopic scale. At this scale, classical physics fails not only
quantitatively but even qualitatively and conceptually.

As if things were not bad enough for classical physics, de Broglie

introduced in 1923 an- other powerful new concept that classical
physics could not reconcile: he postulated that not only does radiation
exhibit particle-like behavior but, conversely, material particles
themselves display wave-like behavior. This concept was confirmed
experimentally in 1927 by Davisson and Germer; they showed that
interference patterns, a property of waves, can be obtained with

material particles such as electrons.

Although Bohr’s model for the atom produced results that agree well
with experimental spectroscopy, it was criticized for lacking the
ingredients of a theory. Like the “quantization” scheme introduced by
Planck in 1900, the postulates and assumptions adopted by Bohr in
1913
1.1. HISTORICAL NOTE 3

were quite arbitrary and do not follow from the first principles of a
theory. It was the dissatis- faction with the arbitrary nature of Planck’s
idea and Bohr’s postulates as well as the need to fit them within the
context of a consistent theory that had prompted Heisenberg and
Schrödinger to search for the theoretical foundation underlying these
new ideas. By 1925 their efforts paid off: they skillfully welded the
various experimental findings as well as Bohr’s postulates into a
refined theory: quantum mechanics. In addition to providing an
accurate reproduction of the existing experimental data, this theory
turned out to possess an astonishingly reliable predic- tion power
which enabled it to explore and unravel many uncharted areas of the
microphysical world. This new theory had put an end to twenty five
years (1900–1925) of patchwork which was dominated by the ideas of
Planck and Bohr and which later became known as the old

quantum theory.

Historically, there were two independent formulations of quantum

mechanics. The first formulation, called matrix mechanics, was
developed by Heisenberg (1925) to describe atomic structure starting
from the observed spectral lines. Inspired by Planck’s quantization of
waves and by Bohr’s model of the hydrogen atom, Heisenberg
founded his theory on the notion that the only allowed values of energy
exchange between microphysical systems are those that are discrete:
quanta. Expressing dynamical quantities such as energy, position,
momentum and angular momentum in terms of matrices, he obtained
an eigenvalue problem that describes the dynamics of microscopic
systems; the diagonalization of the Hamiltonian matrix yields the
energy spectrum and the state vectors of the system. Matrix
mechanics was very successful in

accounting for the discrete quanta of light emitted and absorbed by

atoms.

The second formulation, called wave mechanics, was due to

Schrödinger (1926); it is a generalization of the de Broglie postulate.
This method, more intuitive than matrix mechan- ics, describes the
dynamics of microscopic matter by means of a wave equation, called
the Schrödinger equation; instead of the matrix eigenvalue problem of
Heisenberg, Schrödinger obtained a differential equation. The
solutions of this equation yield the energy spectrum and the wave
function of the system under consideration. In 1927 Max Born
proposed his proba- bilistic interpretation of wave mechanics: he took
the square moduli of the wave functions that

are solutions to the Schrödinger equation and he interpreted them as

probability densities.

These two ostensibly different formulations—Schrödinger’s wave

formulation and Heisen- berg’s matrix approach—were shown to be
equivalent. Dirac then suggested a more general formulation of
quantum mechanics which deals with abstract objects such as kets
(state vec- tors), bras, and operators. The representation of Dirac’s
formalism in a continuous basis—the position or momentum
representations—gives back Schrödinger’s wave mechanics. As for
Heisenberg’s matrix formulation, it can be obtained by representing
Dirac’s formalism in a discrete basis. In this context, the approaches of
Schrödinger and Heisenberg represent, re- spectively, the wave
formulation and the matrix formulation of the general theory of
quantum mechanics.

Combining special relativity with quantum mechanics, Dirac derived in

1928 an equation which describes the motion of electrons. This
equation, known as Dirac’s equation, predicted the existence of an
antiparticle, the positron, which has similar properties, but opposite
charge, with the electron; the positron was discovered in 1932, four
years after its prediction by quan-

tum mechanics.

In summary, quantum mechanics is the theory that describes the

dynamics of matter at the microscopic scale. Fine! But is it that
importantto learn? Thisisno less than an otiose question, for quantum
mechanics is the only valid framework for describing the microphysical
world.

It is vital for understanding the physics of solids, lasers, semiconductor

and superconductor
4 CHAPTER 1. ORIGINS OF QUANTUM PHYSICS

devices, plasmas, etc. In short, quantum mechanics is the founding basis of all
modern physics: solid state, molecular, atomic, nuclear, and particle physics, optics,
thermodynamics, statistical mechanics, and so on. Not only that, it is also considered
to be the foundation of chemistry and biology.

Zettili, Nouredine.
Quantum Mechanics: concepts and applications / Nouredine Zettili. – 2nd ed.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-470-02678-6 (cloth: alk. paper) – ISBN 978-0-470-02679-3 (pbk.: alk. paper)
1. Quantum theory. I. Title
QC174.12.Z47 2009
530.12 – dc22
Quantum Theory:
Concepts and

Methods

by

Asher Peres

Department of Physics,

Technion-Israel Institute of Technology,

Haifa, Israel

KLUWER ACADEMIC PUBLISHERS

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INTRODUCTION TO

QUANTUM MECHANICS

A. C. Phillips

Department of Physics and Astronomy

University of Manchester

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We now accept the fact that electrons occupy only certain energy
levels in atoms. In most atoms, some of the energy differences between
levels correspond to the energy of visible light. Thus, colors associated
with electronic transitions in such elements can be
observed by the human eye.
 Although the Bohr theory satisfactorily explained the spectra of
hydrogen and of other species containing one electron (He_, Li2_, etc.)
the wavelengths in the observed spectra of more complex species
could not be calculated. Bohr’s assumption of circular orbits was
modified in 1916 by Arnold Sommerfeld (1868–1951), who assumed
elliptical orbits. Even so, the Bohr approach was doomed to failure,
because it modified classical mechanics to solve a problem that could
not be solved by classical mechanics. It was a contrived solu- tion. This
failure of classical mechanics set the stage for the development of a
new physics, quantum mechanics, to deal with small particles. The
Bohr theory, however, did intro- duce the ideas that only certain energy
levels are possible, that these energy levels are
described by quantum numbers that can have only certain allowed
values, and that the quantum numbers indicate something about where
and how stable the electrons are in these energy levels. The ideas of
modern atomic theory have replaced Bohr’s original theory. But his
achievement in showing a link between electronic arrangements and
Balmer and Rydberg’s empirical description of light absorption, and in
establishing the quantiza- tion of electronic energy, was a very
important step toward an understanding of atomic
structure.
Two big questions remained about electrons in atoms: (1) How are
electrons arranged in atoms? (2) How do these electrons behave? We
now have the background to consider how modern atomic theory
answers these questions.

Whitten, Davis, Peck _ General Chemistry

 2000

Principles of quantum theory

The role—indeed, the existence—of quantum mechanics was appreciated only during the twentieth century.
Until then it was thought that the motion of atomic and subatomic particles could be expressed in terms of the
laws of classical mechanics introduced in the seventeenth century by Isaac Newton (see Funda- mentals F.3),
for these laws were very successful at explaining the motion of planets and everyday objects such as pendulums
and projectiles. Classical physics is based on three ‘obvious’ assumptions:
1. A particle travels in a trajectory, a path with a precise position and momen- tum 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 assumptions agree with everyday experience. For example, a pendulum swings with a precise
oscillating motion and can be made to oscillate with any energy simply by pulling it back to an arbitrary angle
and then letting it swing freely. Classical mechanics lets us predict the angle of the pendulum and the speed at
which it is swinging at any instant.
Towards the end of the nineteenth century, experimental evidence accumu-
lated showing that classical mechanics failed to explain all the experimental
evidence on very small particles, such as individual atoms, nuclei, and
electrons. It took until 1926 to identify the appropriate concepts and equations
for describ- ing them. We now know that classical mechanics is in fact only an
approximate description of the motion of particles and the approximation is
invalid when it is applied to molecules, atoms, and electrons.
Library of Congress Number: 2010940703
© 2006, 2011 by P.W. Atkins and J. de Paula
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Printed in Italy by L.E.G.O. S.p.A
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ISBN-10: 1-4292-3114-9
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ISBN: 978-0-19-956428-6

Physical Chemistry
for the Life Sciences
Second edition

Peter Atkins
Professor of Chemistry, Oxford University
Julio de Paula
Professor of Chemistry, Lewis & Clark College
College Physics